Process for cracking hydrocarbons with a crystalline zeolite



United States Patent 3,140,251 PROCESS FOR CRACKING HYDROCARBONS WITH ACRYSTALLINE ZEOLITE Charles J. Plank, Woodbury, and Edward J. Rosinski,

Almonesson, N.J., assignors to Socony Mobil Oil Company, Inc. acorporation of New York No Drawing. Filed Dec. 21, 1961, Ser. No.161,241

19 Claims. (Cl. 208-420) This invention relates to the catalyticconversion of hydrocarbons and more particularly to the catalyticcrackmg of high boiling hydrocarbon oils into hydrocarbons of lowerboiling range in the presence of a new and improved catalyst.

A wide variety of materials have heretofore been proposed as catalystsfor the cracking of high boiling hydrocarbons, such as gas oils, toppedcrudes, reduced crudes or similar materials, into lower boilinghydrocarbons boiling in the motor fuel range. The cracking catalystsmost Widely used'are solid materials which behave in an acidic manner.Although catalysts of this type possess one or more desiredcharacteristics, a great many of the acidic catalysts have undesirablecharacteristics, such as lack of thermal stability, availability, ormechanical strength, etc., whereby a wide range of suitable propertiescannot be maintained. Synthetic silica-alumina composites, the mostpopular catalysts known to have been proposed heretofore, providelimited yields of gasoline for a given yield of coke and further sufferthe disadvantage of rapidly deteriorating and becoming inactive in thepresence of steam, particularly at temperatures above 1000 F. Othercatalysts less widely used are materials of an argillaceous nature,e.g., bentonite and montmorillonite, which have been treated with acidto bring out their latent cracking characteristics. Catalysts of thisgeneral type are relatively inexpensive, but are only moderately activeand exhibit a decline in activity over periods of many conversion andregeneration cycles. Some synthetic materials, such as silica-magnesiacomplexes, are more active than conventional silica-alumina catalystsand undergo normal aging, but have limited utility because of their poorproduct distribution as evidenced, for example, by low octane number ofthe gasoline.

Other disadvantages of heretofore proposed cracking catalysts includepoor activity, chemical stability and product distribution in obtainingdesired yields of useful products.

The present invention is based on the discovery that highly activehydrocarbon cracking catalysts can be obtained by admixing an inorganicoxide gel with an aluminosilicate containing a total of 0.5 to 1.0equivalent of ion of positive valence per gram atom of aluminum whereinfrom 0.01 to 0.99 equivalent of said ions are hydrogen ions and from0.99 to 0.01 equivalent of said ions are cations of metals selected fromGroup IB through Group VIII of the Periodic Table. The catalyst of thisinvention possesses a wide spectrum in magnitude ofcatalytic activity;can be used in relatively small concentrations; and permit certainhydrocarbon conversion processes to be carried out under practicable andcontrollable rates at lower temperatures than those previously employed.In the catalytic cracking of hydrocarbon oils into hydrocarbon productsof lower molecular weight, the reaction rates per unit volume ofcatalyst that are obtainable by the catalyst of the invention vary up tomany thousand times the rates achieved With the best siliceous catalystsheretofore proposed. The present invention furthermore provides a meanswhereby aluminosilicate materials having no internally availablesurfaces and only external particle surface areas can be readilyconverted to useful catalysts which thus broadens considerably theirrealm of practical utility.

ice

The high activity catalysts contemplated herein are aluminosilicatecompositions which are strongly acidic in character as a result oftreatment with a fluid medium containing at least one metallic cationand a hydrogen ion or ion capable of conversion to a hydrogen ion.Inorganic and organic acids broadly represent the source of hydrogenions; metallic salts the source of metal cations; and ammonium compoundsthe source of cations capable of conversion to hydrogen ions. Theproduct resulting from treatment with the fluid medium is an activatedcrystalline and/or amorphous aluminosilicate in which the nuclearstructure thereof has been modified solely to the extent of havingprotons and metallic cations chemisorbed or ionically bonded thereto.The activated aluminosilicate contains at least 0.5 equivalent andpreferably contains more than 0.9 equivalent of ions of positive valenceper gram atom of aluminum. Except for alkali metal cations which may bepresent as impurities to the extent of less than 0.25 equivalent pergram atom of aluminum, no other cations of metals of Group IA of thePeriodic Table are associated with the aluminosilicate. Whensubsequently dried, washed and further used as an intermediate, thisproduct has been found to be extremely active as a catalyst forhydrocarbon conversion.

In preparing the catalyst composition, the aluminosilicate can becontacted with a non-aqueous or aqueous fluid medium comprising a gas,polar solvent or water solution containing the desired hydrogen ion orammonium ion capable of conversion to a hydrogen ion and at least onemetallic salt soluble in the fluid medium. Alternatively, thealuminosilicate can be first contacted with a fluid medium containing ahydrogen ion or ammonium ion capable of conversion to a hydrogen ion andthen with a fluid medium containing at least one metallic salt.Similarly, the aluminosilicate can be first contacted with a fluidmedium containing at least one metallic salt and then with a fluidmedium containing a hydrogen ion or an ion ca pable of conversion to ahydrogen ion or a mixture of both. Water is the preferred medium forreasons of economy and ease of preparation in large scale operationsinvolving continuous or batchwise treatment. Similarly, for this reason,organic solvents are less preferred but can be employed providing thesolvent permits ionization of the acid, ammonium compound and metallicsalt. Typical solvents include cyclic and acyclic ethers such asdioxane, tetrahydrofuran, ethyl ether, diethyl ether, diisopropyl ether,and the like; ketones such as acetone and methyl ethyl ketone; esterssuch as ethyl acetate, propyl acetate; alcohols such as ethanol,propanol, butanol, etc.; and miscellaneous solvents such asdimethylformamide, and the like.

The hydrogen ion, metal cation, or ammonium ion may be present in thefluid medium in an amount varying within wide limits dependent upon thepH value of the fluid medium. Where the aluminosilicate material has amolar ratio of silica to alumina greater than about 5.0, the fluidmedium may contain a hydrogen ion, metal cation, ammonium ion, or a.mixture thereof, equivalent to a pH value ranging from less than 1.0 upto a pH value of about 12.0. Within these limits, pH values for fluidmedia containing a metallic cation and/or an ammonium ion range from 4.0to 10.0, and are preferably between a pH value of 4.5 to 8.5. For fluidmedia containing a hydro gen ion alone or with a metallic cation, the pHvalues range from less than 1.0 up to about 7.0, and are preferablywithin the range of less than 1.0 up to 4.5. Where the molar ratio ofthe aluminosilicate is greater than about 2.2 and less than about 5.0,the pH value for the fluid media containing a hydrogen ion or a metalcation ranges from 3.8 to 8.5. Where ammonium ions are employed, eitheralone or in combination with metallic cations, the pH value ranges from4.5 to 9.5 and is preferably within the limit of 4.5 to 8.5. When thealuminosilicate material has a molar ratio of silica to alumina lessthan about 3.0, the preferred medium is a fluid medium containing anammonium ion instead of a hydrogen ion.

In carrying out the treatment with the fluid medium, the procedureemployed comprises contacting the aluminosilicate with the desired fluidmedium or media until such time as metallic cations originally presentin the aluminosilicate are virtually exhausted. Cations of metals ofGroup IA of the Periodic Table, if present in the modifiedaluminosilicate, tend to suppress or limit catalytic properties, theactivity of which, as a general rule, decreases with increasing contentof these metallic cations. Effective treatment with the fluid medium toobtain a modified aluminosilicate having high catalytic activity willvary, of course, with the duration of the treatment and temperature atwhich it is carried out. Elevated temperatures tend to hasten the speedof treatment whereas the duration thereof varies inversely with theconcentration of the ions in the fluid medium. In general, thetemperatures employed range from below ambient room temperature of 24 C.up to temperatures below the decomposition temperature of thealuminosilicate. Following the fluid treatment, the treatedaluminosilicate is washed with water, preferably distilled water, untilthe efiluent wash water has a pH value of wash water, i.e., betweenabout and 8. The aluminosilicate material is thereafter analyzed formetallic ion content by methods well known in the art. Analysis alsoinvolves analyzing the effluent wash for anions obtained in the wash asa result of the treatment, as well as determination of and correctionfor anions that pass into the etfiuent wash from soluble substances ordecomposition products of insoluble substances which are otherwisepresent in the aluminosilicate as impurities.

The actual procedure employed for carrying out the fluid treatment ofthe aluminosilicate may be accomplished in a batchwise or continuousmethod under atmospheric, subatmospheric or superatmospheric pressure. Asolution of the ions of positive valence in the form of a moltenmaterial, vapor, aqueous or nonaqueous solution, may be passed slowlythrough a fixed bed of the aluminosilicate. If desired, hydrothermaltreatment or a correspondingly non-aqueous treatment with polar solventsmay be effected by introducing the aluminosilicate and fluid medium intoa closed vessel maintained under autogenous pressure. Similarly,treatments involving fusion or vapor phase contact may be employedproviding the melting point or vaporization temperature of the acid orammonium compound is below the decomposition temperature of thealuminosilicate.

A wide variety of acidic compounds can be employed with facility as asource of hydrogen ions and include both inorganic and organic acids.

Representative inorganic acids which can be employed include acids suchas hydrochloric acid, hypochlorous acid, chloroplatinic acid, sulfuricacid, sulfurous acid, hydrosulfuric acid, peroxydisulfonic acid (H S Operoxymonosulfuric acid (H 80 dithionic acid (B 5 0 sulfamic acid (H NHSH), amidodisulfonic acid chlorosulfuric acid, thiocyanic acid,hyposulfurous acid (H S O pyrosulfuric acid (H S O thiosulfuric acid (11 5 0 nitrosulfonic acid (HSO -NO), hydroxylamine disulfonic acid ((HSONOH), nitric acid, nitrous acid, hyponitrous acid, carbonic acid and thelike.

Typical organic acids which find utility in the practice of theinvention include the monocarboxylic, dicarboxylic and polycarboxylicacids which can be aliphatic, aromatic or cycloaliphatic in nature.

Representative aliphatic monocarboxylic, dicarboxylic and polycarboxylicacids include the saturated and unsaturated, substituted andunsubstituted acids such as formic acid, acetic acid, bromoacetic acid,propionic acid,

l 2-bromopropionic acid, 3-bromopropionic acid, lactic acid, n-butyricacid, isobutyric acid, crotonic acid, nvaleric acid, isovaleric acid,n-caproic acid, oenanthic acid, pelargonic acid, capric acid, undecyclicacid, lauric acid, myristic acid, palmitic acid, stearic acid, oxalicacid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelicacid, suberic acid, azelaic acid, sebacic acid, alkylsuccinic acid,alkenylsuccinic acid, maleic aid, fumaric acid, itaconic acid,citraconic acid, mesaconic acid, glutonic acid, muconic acid, ethylidenemalonic acid, isoprypylidene malonic acid, allyl malonic acid.

Representative aromatic and cycloaliphatic monocarboxylic, dicarboxylicand polycarboxylic acids include 1,2-cyclohexane-dicarboxylic acid,1,4-cyclohexanedicarboxylic acid, Z-carboxy-Z-methylcyclohexaneaceticacid, phthalic acid, isophthalic acid, terephthalic acid, 1,8-naphthalenedicarboxylic acid, 1,Z-naphthalenedicarboxylic acid,tetrahydrophthalic acid, 3-carboxy-cinnamic acid, hydrocinnamic acid,pyrogallic acid, benzoic acid, ortho, meta and para-methyl, hydroxyl,chloro, bromo and nitro-substituted benzoic acids, phenylacetic acid,mandelic acid, benzylic acid, hippuric acid, benzenesulfonic acid,toluenesulfonic acid, methanesulfonic acid and the like.

Other sources of hydrogen ions include carboxy polyesters prepared bythe reaction of an excess polycarboxylic acid or an anhydride thereofand a polyhydric alcohol to provide pendant carboxyl groups.

Still other materials capable of providing hydrogen ions are ionexchange resins having exchangeable hydrogen ions attached to baseresins comprising cross-linked resinous polymers of monovinyl aromaticmonomers and polyvinyl compounds. These resins are well known materialswhich are generally prepared by copolymerizing in the presence of apolymerization catalyst one or more monovinyl aromatic compounds, suchas styrene, vinyl toluene, vinyl xylene, with one or more divinylaromatic compounds such as divinyl benzene, divinyl toluene, divinylxylene, divinyl naphthalene and divinyl acetylene. Followingcopolymerization, the resins are further treated with suitable acids toprovide the hydrogen form of the resin.

Still another class of compounds which can be employed are ammoniumcompounds which decompose to provide hydrogen ions when analuminosilicate treated with a solution of said ammonium compound issubjected to temperatures below the decomposition temperature of thealuminosilicate.

Representative ammonium compounds which can be employed include ammoniumchloride, ammonium bromide, ammonium iodide, ammonium carbonate,ammonium bicarbonate, ammonium sulfate, ammonium hydroxide, ammoniumsulfide, ammonium thiocyanate, ammonium dithiocarbamate, ammoniumperoxysulfate, ammonium acetate, ammonium tungstate, ammonium molybdate,ammonium benzoate, ammonium borate, ammonium carbamate, ammoniumsesquicarbonate, ammonium chloroplumbate, ammonium citrate, ammoniumdithionate, ammonium fluoride, ammonium gallate, ammonium nitrate,ammonium nitrite, ammonium formate, ammonium propionate, ammoniumbutyrate, ammonium valerate, ammonium lactate, ammonium malonate,ammonium oxalate, ammonium palmitate, ammonium tartarate and the like.Still other ammonium compounds which can be employed include tetraalkyland tetraaryl ammonium salts such as tetramethylammonium hydroxide,trimethylammonium hydroxide. Other compounds which can be employed arenitrogen bases such as the salts of guanidine, pyridine, quinoline, etc.

A wide variety of metallic compounds can be employed with facility as asource of metallic cations and include both inorganic and organic saltsof the metals of Group 1B through Group VIII of the Periodic Table.

Representative of the salts which can be employed include chlorides,bromides, iodides, carbonates, bicarbonates, sulfates, sulfides,thiocyanates, dithiocarbamates, peroxysulfates, acetates, benzoates,citrates, fluorides, nitrates, nitrites, formates, propionates,butyrates, valerates, lactates, malonates, oxalates, palmitates,hydroxides, tartarates and the like. The only limitations on theparticular metal salt or salts employed are that it be soluble in thefluid medium in which it is used and compatible with the hydrogen ionsource, especially if both the metallic salt and the hydrogen ion sourceare in the same fluid medium. The preferred salts are the chlorides,nitrates, acetates and sulfates.

Of the wide variety of metallic salts which can be employed, the mostpreferred are salts of trivalent metals, then of divalent metals andlastly, of monovalent metals. Of the divalent metals, the preferred onesare of Group IIA of the Periodic Table. The particularly preferred saltsare those of the rare earth metals including cerium, lanthanum,praseodymium, neodymium, illinium, samarium, europium, gadolinium,terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutecium.

The rare earth salts employed can either be the salt of a single metalor preferably of mixtures of metals such as a rare earth chloride ordidyrnium chlorides. As hereinafter referred to, a rare earth chloridesolution is a mixture of rare earth chlorides consisting essentially ofthe chlorides of lanthanum, cerium, neodymium and praseodymium withminor amounts of samarium, gadolinium and yttrium. The rare earthchloride solution is commercially available and it contains thechlorides of a rare earth mixture having the relative composition cerium(as CeO 48% by weight, lanthanum (as La O 24% by weight, praseodymium(as Pr O 5% by weight, neodymium (as Nd O 17% by weight, samarium (as SmO 3% by Weight, gadolinium (as Gd O 2% by weight, yttrium (as Y O 0.2%by weight and other rare earth oxides 0.8% by weight. Didymium chlorideis also a mixture of rare earth chlorides, but having a low ceriumcontent. It consists of the following rare earths determined as oxides:lanthanum, 45-46% by weight; cerium 12% by weight; praseodymium, 910% byweight, neodymium, 32-33% by weight; samarium, 5-6% by weight,gadolinium 3-4% by weight, yttrium, 0.4% by weight, other rare earthearths 1-2% by weight. It is to be understood that other mixtures ofrare earths are equally applicable in the instant invention.

Representative metal salts which can be employed, aside from themixtures mentioned above, include silver chloride, silver sulfate,silver nitrate, silver acetate, silver arsinate, silver bromide, silvercitrate, silver carbonate, silver oxide, silver tartrate, calciumacetate, calcium arsenate, calcium benzoate, calcium bromide, calciumcarbonate, calcium chloride, calcium citrate, beryllium bromide,beryllium carbonate, beryllium hydroxide, beryllium sulfate, bariumacetate, barium bromide, barium carbonate, barium citrate, bariummalonate, barium nitrite, barium oxide, barium sulfide, magnesiumchloride, magnesium bromide, magnesium sulfate, magnesium sulfide,magnesium acetate, magnesium formate, magnesium stearate, magnesiumtartrate, zinc sulfate, zinc nitrate, zinc acetate, zinc chloride, zincbromide, aluminum chloride, aluminum bromide, aluminum acetate, aluminumcitrate, aluminum nitrate, aluminum oxide, aluminum phosphate, aluminumsulfate, titanium bromide, titanium chloride, titanium nitrate, titaniumsulfate, zirconium chloride, zirconium nitrate, zirconium sulfate,chromic acetate, chromic chloride, chrornic nitrate, chromic sulfate,ferric chloride, ferric bromide, ferric acetate, ferrous chloride,ferrous arsenate, ferrous lactate, ferrous sulfate, nickel chloride,nickel bromide, cerous acetate, cerous bromide, cerous carbonate, cerouschloride, cerous iodide, cerous sulfate, cerous sulfide, lanthanumchloride, lanthanum bromide, lanthanum nitrate, lanthanum sulfate,lanthanum sulfide, yttrium bromate, yttrium bromide, yttrium chloride,yttrium nitrate, yttrium sulfate, samarium acetate, samarium chloride,samarium bromide, samarium sulfate, neodymium chloride, neodymium oxide,neodymium sulfide, neodymium sulfate, praseodymium chloride,praseodymium bromide, praseodymium sulfate, praseodymium sulfide, etc.

The aluminosilicates treated in accordance with the invention include awide variety of aluminosilicates, both natural and synthetic, which havean amorphous or crystalline structure. These aluminosilicates can bedescribed as a three dimensional framework of $0,, and A10 tetrahedra inwhich the tetrahedra are cross-linked by the sharing of oxygen atomswhereby the ratio of the total aluminum and silicon atoms to oxygenatoms is 1:2. In their hydrated form the aluminosilicates may berepresented by the formula:

wherein M is a cation which balances the electrovalence of thetetrahedra, n represents the valence of the cation, w the moles of SiOand y the moles of H 0. The cation may be any or more of a number ofmetal ions depending on whether the aluminosilicate is synthesized oroccurs naturally. Typical cations include sodium, linthium, p0.-tassium, silver, magnesium, calcium, zinc, barium, iron and manganese.Although the proportions of inorganic oxides in the silicates and theirspatial arrangement may vary, effecting distinct properties in thealuminosilicates, the two main characteristics of these materials is thepresence in their molecular structure of at least 0.5 equivalent of anion of positive valence per gram atom of aluminum, and an ability toundergo dehydration without substantially affecting the SiO., and A10framework. In this respect, these characteristics are essential forobtaining catalyst compositions of high activity in accordance with theinvention.

Representative materials include synthesized crystallinealuminosilicates, designated Zeolite X, which can be represented interms of mole ratios of oxides as follows:

wherein M is a cation having a valence of not more than three, nrepresents the valence of M, and y is a value up to eight depending onthe identity of M and degree of hydration of the crystal. The sodiumform may be represented in terms of mole ratios of oxides as follows:

0.9 Na O:Al O :2.5 SiO :6.l H O (III) Another synthesized crystallinealuminosilicate, designated Zeolite A, can be represented in mole ratiosof oxide as:

1.0;i=0.2M O:AlzOazLBfiiOjSiOzzyHzO wherein M represents a metal, 11 isthe valence of M, and y is any value up to about 6. As prepared, ZeoliteA contains primarily sodium cations and is designated sodium Zeolite A.

Other suitable synthesized crystalline aluminosilicates are thosedesignated Zeolite Y, L and D.

The formula for Zeolite Y expressed in oxide mole ratios is:

0.9 i 0.2Na O :Al O wSiO yH O (V) wherein w is a value ranging from 3 to6 and y may be any value up to about 9.

The composition of Zeolite L in oxide mole ratios may be represented as:

wherein M designates a metal, n represents the valence of M, and y isany value from 0 to 7.

The formula for Zeolite D, in terms of oxide mole ratios, may berepresented as:

0.9: 0.2Na O :A1 O wSiO yH O (VIII) wherein w is from 2.45 to 3.65, andy, in the hydrated form, is about 7.

The formula for Zeolite S in terms of oxide mole ratios may be Writtenas:

0.9i0.2Na O:Al O :wSiO :yH O (IX) wherein w is from 4.6 to 5.9 and y, inthe hydrated form, is about 6 to 7.

The formula for Zeolite T in terms of oxide mole ratios may be writtenas:

6.9-|O.5SiO :yI-I O (X wherein x is any value from about 0.1 to about0.8 and y is any value from about to about 8.

The formula for Zeolite Z in terms of oxide mole ratios may be writtenas:

K20 IA1203 I :yH O

wherein y is any value not exceeding 3.

The formula for Zeolite E in terms of oxide mole ratios may be writtenas:

0,910.11 2 01111203:1.95i0lSiO2z1/Hg0 (XII) wherein M is a cation, 11 isthe valence of the cation, and

y is a value of O to 4.

The formula for Zeolite F in terms of oxide mole ratios may be Writtenas follows:

wherein M is a cation, n is the valence of the cation, and y is anyvalue from 0 to about 3.

The formula for Zeolite Z, expressed in terms of oxide mole ratios, maybe written as:

wherein M is a cation, 12 is the valence of the cation, and y is anyvalue from 0 to 5.

The formula for Zeolite B may be written in terms of oxide mole ratiosas:

wherein M represents a cation, 11 is the valence of the cation and y hasan average value of 5.1 but may range from O to 6.

Other synthesized crystalline aluminosilicates include those designatedas ZK4 and ZK-S.

ZK-4 can be represented in terms of mole ratios of oxides as:

0.1 to 0.3R:9.7 to 1.0M 2 O2Alz0a22.5 to 4.0Si0z: yH O (XVI) wherein Ris a member selected from the group consisting of methylammonium oxide,hydrogen oxide and mixtures thereof with one another, M is a metalcation, 11 is the valence of the cation, and y is any value from 8 about3.5 to about 5.5. As synthesized, Zeolite ZK-4 contains primarily sodiumcations and can be represented by unit cell formula:

The major lines of the X-ray diffraction pattern of ZK-4 are set forthin the table below:

ZK-4 can be prepared by preparing an aqueous solution of oxidescontaining as Na O, A1 0 SiO H 0 and tetramethylammonium ion having acomposition, in terms of oxide mole ratios, which falls within thefollowing ranges:

Slog/A1203 2.5 to 11 maintaining the mixture at a temperature of aboutC. to C. until the crystals are formed, and separating the crystals fromthe mother liquor. The crystal material is thereafter washed until thewash efiluent has a pH essentially that of wash water and subsequentlydried.

ZK-5 is representative of another crystalline aluminosilicate which isprepared in the same manner as Zeolite ZK-4'except thatN,N-dimethyltriethylenediammonium hydroxide is used in place oftetramethylammonium hydroxide. ZK-5 may be prepared from an aqueoussodium aluminosilicate mixture having the following compositionexpressed in terms of oxide mole ratios as:

The N,N-dimethyltriethylenediammonium hydroxide used in preparing ZK-Scan be prepared by methylating 1,4-diazobicyclo-(2.2.2)-octane withmethyl iodide 01' dimethyl sulfate, followed by conversion to thehydroxide by treatment with silver oxide or barium hydroxide. Thereaction may be illustrated as:

In using the N,N-dimethyltriethylene-diammonium hydroxide compound inthe preparation of ZK-S, the hydroxide may be employed per se, orfurther treated with a source of silica, such as silica gel, andthereafter reacted with aqueous sodium aluminate in a reaction mixturewhose chemical composition corresponds to the above-noted oxide moleratios. Upon heating at temperatures of about 200 to 600 C., the methylammonium ion is converted to hydrogen ion.

Among the naturally occurring crystalline aluminosilicates which can beemployed for purposes of the invention are included levynite, erionite,faujasite, analcite, paulingite, noselite, ferriorite, heulandite,scolecite, stilbite, clinoptilolite, harmotome, phillipsite,brewsterite, flakite, datolite, and aluminosilicates represented asfollows:

Chabazite, Na O.A1 O .4SiO .6H O Gmelinite, Na O.A1 O .4SiO .6I-I OCancrinite, 3 (Na O.A1 O .2SiO .Na CO Leucite, K20.A1203.4Si02 Lazurite,(Na,Ca) Al Si O 4.2(S,Cl,So Scapolite, Na Al Si O .C1

Ptilolite, N320.A1203. Mesolite, Na O.A1 O .3SiO .2-3H O Mordenite, NaO.Al O .10SiO .6.6H O Nepheline, Na O.Al O .2SiO

Natrolite, Na O.Al O .3SiO .2H O Sodalite, 3 (Na O.Al O .2SiO .2NaClOther'aluminosilicates which can be used are caustic treated clays.

Of 'the clay materials, montmorillonite and kaolin families arerepresentative types which include the subbentonites, such as bentonite,and the kaolins commonly identified as Dixie, McNamee, Georgia andFlorida clays in which the main mineral constituent is halloysite,kaolinite, dickite, nacrite, or anauxite. Such clays may be used in theraw state as originally mined or initially subjected to calcination,acid treatment or chemical modification. In order to render the clayssuitable for use, however, the clay material is treated with sodiumhydroxide or potassium hydroxide, preferably in admixture with a sourceof silica, such as sand, silica gel or sodium silicate, and calcined attemperatures ranging from 230 to 1600 F. Following calcination, thefused material is crushed, dispersed in water and digested in theresulting alkaline solution. During the digestion, materials withvarying degrees of crystallinity are crystallized out of solution. Thesolid material is separated from the alkaline material and thereafterwashed and dried. The treatment can be effected by reacting mixturesfalling within the following weight ratios:

Na O/ clay (dry basis) 1.0-6.6 to 1 SiO clay (dry basis) 001-3 .7 to 1 HO/Na O (mole ratio) 35-180 to 1 As previously noted, the activealuminosilicates used for purposes of the invention are characterized ashaving at least 0.5 equivalent of an ion of positive valence per gramatom of aluminum, as determined by base exchanging with other cations byrecognized techniques. Aluminosilicate starting materials not possessingthis characteristic, however, may be employed providing they are eitherpretreated or acquire this characteristic as a result of treatment witha fluid medium. As an example of pretreatment, argillaceous materialscontacted with caustic or caustic-silica mixtures, as above described,results in the formation of amorphous and/ or crystallinealuminosilicates having at least 0.5 equivalent, usually about 1.0equivalent, or cation per gram atom of aluminum. Similarly, treatment ofan amorphous silica-alumina composite with a fluid medium containing anammonium ion capable of conversion to a hydrogen ion, for example,tetramethylammonium hydroxide, also results in an increase in the cationconcentration per gram atom of aluminum to values above 0.5 equivalent.

The preparation of aluminosilicate compositions in ac cordance with theinvention provides a means for obtaining exceptionally good catalysts.While the aluminosilicate component may contain varying amounts ofsilicon and aluminum, it has been found that extremely good results canbe obtained through use of crystalline aluminosilicates having atomicratios of silicon to aluminum greater than 1.1, preferably greater than1.67, and more preferably above 2.7. Preferred aluminosilicates thusinclude natural materials such as gmelinite, chabazite and mordenite,and synthetic crystalline aluminosilicates such as Zeolites X, Y, T,ZK-4, and ZK-5.

The active aluminosilicate component prepared in the foregoing manner iscombined, dispersed or otherwise intimately admixed with an inorganicoxide gel which serves as a base, binder, matrix or promoter, in suchproportions that the resulting product contains from about 2 to byweight and preferably about 5 to 50% by weight of the aluminosilicate inthe final composite. The resulting aluminosilicate-inorganic oxide gelcomposition is then preferably precalcined in an inert atmosphere nearthe temperature contemplated for conversion but may be calcinedinitially during use in the conversion process. Generally, the catalystcomposition is dried between F. and 600 F., and thereafter calcined inair or an inert atmosphere of nitrogen, hydrogen, helium, flue gas orotherinert gas at temperatures ranging from about 500 F. to 1500 F. forperiods of time ranging from 1 to 48 hours or more. It is to beunderstood that the active aluminosilicate component can be calcinedprior to incorporation with the inorganic oxide gel.

The aluminosilicate-ino-rganic oxide gel compositions can be prepared byseveral methods wherein the aluminosilicate having a particle size lessthan 40 microns, preferably within the range of 2 to 7 microns, isintimately admixed with the inorganic oxide gel while the latter is in ahydrous state such as in the form of a hydrosol, hydrogel, Wetgelatinous precipitate, or a mixture thereof. Thus, finely dividedactive aluminosilicate can be mixed directly with a siliceous gel formedby hydrolyzing a basic solution of alkali metal silicate with an acidsuch as hydrochloric, sulfuric, etc. The mixing of the two componentscan be accomplished in any desired manner, such as in a ball mill orother types of kneading mills. The aluminosilicate also may be dispersedin a hydrosol obtained by reacting an alkali metal silicate with an acidor I l 7 an alkaline coagulent. The hydrosol is then permitted to set inmass to a hydrogel which is thereafter dried and broken into pieces ofdesired shape, or dispersed through a nozzle into a bath of oil or otherwater-immiscible suspending medium to obtain spheroidally shaped beadparticles of catalyst such as described in US. Patent No. 2,3 84,946.The aluminosilicate-siliceous gel thus obtained is washed free ofsoluble salts and thereafter dried and/ or calcined as desired. Thetotal alkali metal content of the resulting composite, including alkalimetals which may be present in the aluminosilicate as an impurity, isless than about 4% and preferably less than about 3% by weight based onthe total composition.

In a like manner, the active aluminosilicate may be incorporated with analuminiferous oxide. Such gels are well known in the art and may beprepared, for example, by adding ammonium hydroxide, ammonium carbonate,etc., to a salt of nitrate, etc., in an amount sufiicient to formaluminum hydroxide which upon drying is converted to alumina. Thealuminosilicate may be incorporated with the alurniniferous oxide whilethe latter is in the form of hydrosol, hydrogel or wet gelatinousprecipitate.

The inorganic oxide gel may also consist of a plural gel comprising apredominant amount of silica with one or more metals or oxides thereofselected from Groups IB, II, III, IV, V, VI, VII and VIII of thePeriodic Table. Particular preference is given to plural gels of silicawith metal oxides of Groups IIA, IIIB and IVA of the Periodic Tablewherein the metal oxide is magnesia, alumina, zirconia, beryllia orthoria. The preparation of plural gels is well known and generallyinvolves either separate precipitation or coprecipitation techniques inwhich a suitable salt of the metal oxide is added to an alkali metalsilicate and an acid or base, as required, is added to precipitate thecorresponding oxide. The silica content of the siliceous gel matrixcontemplated herein is generally Within the range of 55 to 100 Weightpercent with the metal oxide content ranging from to 45 percent. Minoramounts of promoters or other materials which may be present in thecomposition include cerium, chromium, cobalt, tungsten, uranium,platinum, lead, zinc, calcium, magnesium, lithium, nickel and theircompounds as well as silica, alumina, or other siliceous oxidecombination as fines.

As a further embodiment of the invention, aluminosilicate catalystshaving exceptionally high orders of activity can be prepared byincorporating a metal aluminosilicate in an inorganic oxide gel matrix,and thereafter contacting the aluminosilicate with the above-mentionedfiuid medium containing a hydrogen ion or ammonium ion capable ofconversion to a hydrogen ion. The treatment is carried out for asufiicient period of time under conditions previously described forobtaining active aluminosilicates. It has been found that catalystsprepared in this manner are extremely active for hydrocarbon conversion,and particularly in the cracking of hydrocarbon oils whereinexceptionally high ratios of gasoline to low grade products, such ascoke and gas, are obtained.

It has been further found in accordance with the invention thatcatalysts of improved activity and having other beneficial properties inthe conversion of hydrocarbons are obtained by subjecting the treatedaluminosilicate to a mild steam treatment carried out at elevatedtemperatures of 800 F. to 1500 F., preferably at temperatures of about1000 F. to 1300 F. The treatment may be accomplished in an atmosphere of100% steam or in an atmosphere consisting of steam and a gas which issubstantially inert to the aluminosilcate. The steam treatmentapparently provides beneficial properties in the aluminosilicate.

The high catalytic activities obtanied by alumnosilcate compositionsprepared in accordance with the invention are illustrated in connectionwith the cracking of a representative hydrocarbon charge. In theexamples hereinafter set forth, the reference catalyst employedconsisted of a conventional silica-alumina bead type cracking catalyst.The silica-alumina catalyst contained about 10 weight percent A1 0 andthe remainder SiO In some instances it also contained a trace amount ofCr O i.e., about 0.15 weight percent.

The cracking activity of the catalyst is further illustrated by itsability to catalyze the conversion of a Mid- Continent gas oil having aboiling range of 450-950 F. to gasoline having an end point of 410 F.Vapors of the gas oil are passed through the catalyst at temperatures of875 F. or 900 F. substantially at atmospheric pressure at a feed rate of1.5 to 16.0 volumes of liquid oil per volume of catalyst per hour forten minutes. The method of measuring the instant catalyst was to comparethe various product yields obtained with such catalyst with yields ofthe same products given by conventional silica-alumina catalyst at thesame conversion level. The differences (A values) shown hereinafterrepresent the yields given by the present catalyst minus yields given bythe conventional catalyst. In these tests the catalyst composition ofthe invention was precalcined at about 1000 F. prior to their evaluationas a cracking catalyst.

Cracking operations carried out with the catalysts prepared inaccordance With the invention may be effected at temperatures rangingfrom about 700 F. to 1200 F.

'under reduced atmospheric or superatmospheric pressure. The catalystcan be utilized in the form of spheroidal particles or beads disposed ina stationary bed, or in the fluid procedures wherein the catalyst isdisposed in a reaction zone to which catalyst is continuously added andfrom which catalyst is continuously removed. A particularly efiectivecracking process can be achieved when the catalyst is used to obtain theinherent advantages realized in the moving bed technique referred to asthe Thermofor catalytic cracking process.

Example 1 A synthetic crystalline aluminosilicate identified as Zeolite13X was subjected to 12 two-hour treatments at 180 F. with an aqueoussolution containing 5% by weight mixture of rare earth chlorides and 2%by weight of ammonium chloride. The aluminosilicate was then Washed withwater until there were no chloride ions in the effiuent, dried, and thentreated for 20 hours at 1225 F. with atmospheric steam to yield acatalyst having a sodium content of 0.31 weight percent.

The following table shows the cracking data obtained when the catalystwas evaluated for cracking gas oil at 900 F.:

TABLE 1 Cracking data:

Conversion, vol. percent 60.9 LHSV 1.6 10 R.V.P. gaso., vol. percent54.6 Excess C s, vol. percent 9.5 C gasoline, vol. percent 51.7 Total Cs, vol. percent 12.5 Dry gas, Wt. percent 5.6 Coke, wt. percent 2.3 Hwt. percent 0.02 A advantage:

10 R.V.P., vol. percent +9.3 Excess C s, vol. percent -4.5 C gasoline,vol. percent +7.4 Total C s, vol. percent -3.7 Dry gas, wt. percent 2.2Coke, Wt. percent 2.4

Example 2 The procedure of Example 1 Was repeated with the exceptionthat the crystalline aluminosilicate was subjected to a continuoustreatment for 24 hours instead of 13 12 two-hour treatments. Thefollowing table shows the cracking data obtained with the catalyst wasevaluated for cracking gas oil at 900 F.:

TABLE 2 Cracking data:

Conversion, vol. percent 60.7 LHSV 16 10 R.V.P. gaso., vol. percent 51.7Excess C s, vol. percent 11.2 C gasoline, vol. percent 49.2 Total C s,vol. percent 13.7 Dry gas, wt. percent 6.4 Coke, wt. percent 3.0 H wt.percent 0.03 A advantage:

R.V.P. gaso., vol. percent +6.5 Excess C s, vol. percent 2.8 C gasoline,vol. percent +6.2 Total C s, vol. percent 2.5 Dry gas, wt. percent 1.3Coke, wt. percent 1.7

Example 3 A crystalline aluminosilicate identified as Zeolite 13X wassubjected to three 2-hour treatments with a 5% by weight aqueoussolution of ammonium chloride and then treated for 48 hours with anaqueous solution consisting of 5% by weight mixture of rare earthchlorides and 2% by Weight of ammonium chloride. The aluminosilicate wasthen washed with water until there were no chloride ions in theefiiuent, dried and then treated for 24 hours at 1200 F. with steam at15 p.s.i.g. to yield a catalyst having a sodium content of 0.2 weightpercent.

Example 4 A synthetic crystalline aluminosilicate identified as Zeolite13X was treated for 72 continuous hours with an aqueous solutioncontaining 10% by weight of ammonium chloride, 10% by weight of ammoniumacetate, and 1% by weight of rare earth chlorides. The aluminosilicatewas then washed with water until there were no chloride or acetate ionsin the efiluent, dried and then treated for 24 hours at 1200 F. withsteam at a pressure of 15 p.s.i.g.

The following table shows the cracking data obtained when the catalystwas evaluated for cracking gas oil at 900 F.:

TABLE 3 Cracking data:

Conversion, vol. percent 56.6 LHSV 16 10 R.V.P. gaso., vol. percent 50.9Excess C s, vol. percent 9.2 C gasoline, vol. percent 48.3 Total C s,vol. percent 11.8 Dry gas, wt. percent 5.4 Coke, wt. percent 1.4 H wt.percent 0.01 A advantage:

1O R.V.P. gaso., vol. percent +7.9 Excess C s, vol. percent -.3.4 Cgasoline, vol. percent +7.4 Total C s, vol. percent 3.0 Dry gas, wt.percent +1.6 Coke, wt. percent 2.5

Example 5 content of 0.36 weight percent.

14 The following table shows the cracking data obtained when thecatalyst was evaluated for cracking gas oil at 900 F.:

TABLE 4 5 Cracking data:

Conversion, vol. percent 63.1 LHSV 16 10 R.V.P. gaso., vol. percent 52.6Excess C s, vol. percent 12.3 10 C gasoline, vol. percent 50.4 Total Cs, vol. percent 14.5 Dry gas, wt. percent 6.8 Coke, wt. percent 3.6 Hwt. percent 0.04 15 A advantage:

10 R.V.P., vol. percent +6.2 Excess C s, vol. percent 2.7 C gasoline,vol. percent +6.2 20 Total C s, vol. percent 2.5 Dry gas, wt. percent1.4 Coke, wt. percent -1.5

Example 6 The procedure of Example 5 was repeated with the exceptionthat the aluminosilicate was steamed for 24 hours at 1200 F. with steamat 15 p.s.i.g. The cracking data obtained when using this catalyst forcracking gas oil at 900 F. is shown in the following table.

TABLE 5 Cracking data:

Conversion, vol. percent 65.9 LHSV 16 10 R.V.P. gaso., vol. percent 56.5Excess C s, vol. percent 12.1 C gasoline, vol. percent 53.9 Total C s,vol. percent 14.7 Dry gas, wt. percent 6.6 Coke, wt. percent 3.0 40 Hwt. percent 0.03

A advantage:

10 R.V.P., vol. percent +8.8 Excess 04 5, vol. percent +3.9 C gasoline,vol. percent +8.4 Total C s, vol. percent 3.3 Dry gas, wt. percent 2.1Coke, wt. percent 2.7

Example 7 The procedure of Example 6 was repeated with the exceptionthat 36 two-hour contacts of the lanthanum chloride and ammoniumchloride solution were employed instead of 24 two-hour contacts. Theresulting catalyst had a sodium content of 0.46 weight percent. Table 6shows the cracking data obtained when the catalyst was evaluated forcracking gas oil at 900 F.

TABLE 6 Cracking data: Conversion, vol. percent 63.7 LHSV 16 10 R.V.P.gaso., vol. percent 55.3 Excess C s, vol. percent 8.1 C gasoline, vol.percent 51.8 Total C s, vol. percent 11.6 Dry gas, wt. percent 7.6 Coke,wt. percent 3.1 H wt. percent 0.0 3

A advantage: 79 10 R.V.P., vol. percent +8.7 Excess C s, vol. percent7.0 C gasoline, vol. percent +7.3 Total C s, vol. percent 5.7 Dry gas,wt. percent 0.7 Coke, wt. percent +2.2

Example 8 A synthetic crystalline aluminosilicate identified as Zeolite13X was treated with an aqueous solution containing 2% by weight mixtureof rare earth chlorides for 18 continuous hours and then treated with anaqueous solution of ammonium sulfate containing by weight of ammoniumsulfate for 3 contacts of 16 hours each and then with 9 contacts of 2hours each of the same solution. The treated aluminosilicate was washedwith water until the efiluent contained no chloride or sulfate ions,dried and then treated for 30 hours at 1200" F. with steam at 15p.s.i.g. The resulting catalyst contained 0.12 weight percent sodium.The catalytic evaluation of the aluminosilicate for cracking gas oil at900 F. is shown in the following table.

TABLE 7 Cracking data:

Conversion, vol. percent 37.5 LHSV 4 R.V.P. gaso., vol. percent 32.5Excess C s, vol. percent 6.5 C gasoline, vol. percent 30.9 Total C s,vol. percent 8.1 Dry gas, Wt. percent 4.1 Coke, wt. percent 1.4 H wt.percent 0.02

A advantage:

10 R.V.P., vol. percent +0.1 Excess C s, vol. percent 0.5 C gasoline,vol. percent +0.9 Total C s, vol. percent --l.4 Dry gas, wt. percent+0.1 Coke, wt. percent -0.2

Example 9 A synthetic crystalline aluminosilicate identified as ZeoliteY was treated with an aqueous solution consisting of 5% by weightmixture of rare earth chlorides and 2% by weight of ammonium chlorideand then washed with water until the effiuent contained no chlorideions, dried and then treated for 24 hours at 1200 F. with p.s.i.g.steam. The resulting aluminosilicate contained 0.52 weight percentsodium and gave the following results when tested for cracking gas oilat 900 F.

TABLE 8 Cracking data:

Conversion, vol. percent 61.6 LHSV 16 10 R.V.P. gaso., vol. percent 54.9Excess C s, vol. percent 9.8 C gasoline, vol. percent 52.1 Total C s,vol. percent 12.5 Dry gas, wt. percent 6.1 Coke, wt. percent 1.9 H wt.percent 0.02

A advantage:

10 R.V.P., vol. percent +9.0

Excess C s, vol. percent 4.6 C gasoline, vol. percent +8.6 Total C s,vol. percent 4.1 Dry gas, wt. percent 1.8 Coke, wt. percent 2.9

Example 10 The procedure of Example 9 was repeated with the exceptionthat the solution consisted of 5% by weight of calcium chloride and 2%by weight of ammonium chloride. The catalytic evaluation for crackinggas oil at 900 F. is shown in the following table.

TABLE 9 Cracking data:

Conversion, vol. percent 61.8 LHSV 10 10 R.V.P. gaso., vol. percent 57.0Excess C s, vol. percent 9.5 C gasoline, vol. percent 54.0 Total C s,vol. percent 12.5 Dry gas, wt. percent 4.8 Coke, wt. percent 1.5 H wt.percent 0.01

A advantage:

10 R.V.P., vol. percent +11.2 Excess C s, vol. percent 4.9 C gasoline,vol. percent +10.4 Total C s, vol. percent 4.1 Dry gas, wt. percent 3.2Coke, wt. percent 3.3

Example 11 The procedure of Example 9 was repeated with the exceptionthat the treatment solution consisted of 5% by weight of lanthanumchloride and 2% by weight of ammonium chloride. The catalytic evaluationfor cracking gas oil at 900 F. is shown in the following table:

TABLE 10 Cracking data:

Conversion, vol. percent 66.1 LHSV 16 10 R.V.P. gaso., v01. percent 59.0Excess C s, vol. percent 9.3 C gasoline, vol. percent 55.7 Total C s,vol. percent 12.6 Dry gas, wt. percent 7.0 Coke, wt. percent 2.3 H wt.percent 0.02 A advantage:

1O R.V.P., vol. percent +11.2 Excess C s, vol. percent 6.9 C gasoline,vol. percent ..+10.1 Total C s, vol. percent 5.7 Dry gas, Wt. percent1.7 Coke, wt. percent 3.4

Example 12 A synthetic crystalline aluminosilicate was prepared bymixing the following solutions:

(A) Sodium silicate solution:

N-Brand sodium silicate 1 77.5 lbs. NaOH pellets 11.0 lbs. Water 143.0lbs. Specific gravity 1.172 at 68 F.

8.8 weight percent NazO, 28.5 weight percent S102, 62.7 weight percentwater.

(B) Sodium aluminate solution:

Sodium aluminate 25.6 lbs. Sodium hydroxide pellets 11.0 lbs. Water195.0 lbs. Specific gravity 1.140 at 68 F.

Solution (B) was added to solution (A) while agitating vigorously tobreak up the hydrogel as it formed into a creamy slurry. The slurry washeated for 12 hours at 205 F., filtered, washed to 11 pH and then driedin air at 280 F. to yield a crystalline aluminosilicate.

3.3 pounds of the aluminosilicate was treated with 4 batches of a 27.5%by weight aqueous solution of calcium chloride, each bath having 1 lb.of calcium chloride per pound of aluminosilicate. Three treatments werefor 24 hours each at 180 F. and the fourth one was for 72 hours at roomtemperature. After the four treatments with the calcium chloridesolution, the aluminosilicate was further treated four times with anaqueous solution containing 2% by weight of calcium chloride and 1% byweight of aluminum chloride for 4 contacts, 3 of which were for 2 hoursand 1 was overnight, all 4 contacts being at room temperature. Thealuminosilicate was then washed with water until the efiiuent containedno chloride ions, dried, pelleted to /2" size, ground to mesh andcalcined for 10 hours in air at 1000 F. The aluminosilicate catalyst wasthen treated with 100% steam at 1225 F. for 20 hours at atmosphericpressure. The resulting catalyst was evaluated for cracking gas oil at875 F. and gave the following results.

TABLE 11 Cracking data:

Conversion, vol. percent 64.3 LHSV 7.5 C gaso., vol. percent 53.5 TotalC s, vol. percent 12.7 Total dry gas, wt. percent 5.0 Coke, wt. percent4.6

A advantage:

C gaso-., vol. percent +11.8 Total C s, vol. percent 8.4 Total dry gas,wt. percent 3.6 Coke, wt. percent -1.0

Example 13 A synthetic crystalline aluminosilicate identified as Zeolite4A was treated three times for 24 hours and one time for 72 hours with a26 weight percent aqueous solution of calcium chloride at 180 F. Afterthe treatment with calcium chloride, the aluminosilicate was thentreated for three two-hour contacts and one overnight contact at roomtemperature with an aqueous solution consisting of 2% by weight ofcalcium chloride and 1% by weight ammonium chloride. The aluminosilicatewas then washed with water until the eflluent contained no chlorideions, dried, calcined for hours at 1000 F. in air, and then treated withsteam for hours at 1225 F. to yield a catalyst having a sodium contentof 0.6 percent by weight.

Example 1 4 A synthetic crystalline aluminosilicate identified asZeolite 5A was treated with a chloroplatinic acid solution containing2.0 grams platinum and an ammonium hydroxide solution containing 28% byweight ammonia. The aluminosilicate was washed with water until theeflluent contained no chloride ions, dried and then treated for 20 hoursat 1225 F. with atmospheric steam to yield an aluminosilicate havingexcellent catalytic properties.

Example 15 1800 grams of a crystalline aluminosilicate identified asZeolite 13X Was treated with a solution consisting of cerium chlorideand ammonium hydroxide. The treatment was carried out at a temperatureof 160-180 F. for /2 hour after which time the slurry was filtered andthen the operation repeated for another /2 hour. The resultingaluminosilicate contained 0.81 weight percent sodium and 24.7 weightpercent cerium.

Example 16 66.5 grams of a synthetic crystalline aluminosilicateidentified as Zeolite 5A was pelleted and treated with 26.6 grams ofammonium nitrate dissolved in 1 gallon of distilled water. The productwas rinsed with distilled water until the efliuent contained no nitrateions and then calcined at 650-700 F. for several hours in a stream ofnitrogen. The resulting aluminosilicate analyzed at 9.08 weight percentcalcium.

Example 17 A natural crystalline aluminosilicate identified as gmelinitewas crushed to a particle size of less than 32 mesh and calcined in airfor 2 hours at 650 F. 5 grams of the calcined crushed gmelinite wastreated 10 times with 10 cc. of a solution containing 4% by weightmixture of rare earth chlorides and 1% by weight ammonium chloride. Eachof the treatments was for 1 hour at a temperature of 173l86 F. Thealuminosilicate was then washed with water until the effluent containedno chloride ions, dried overnight at 190 F., pelleted, recrushed to aparticle size of less than 12 mesh and calcined for three hours at 900F. in air. The resulting product was employed as a catalyst for thecracking of decane at a catalyst concentration of 3.3 cc., at a feedrate of 3.0 LHSV, and temperature of 900 F. A conversion of 91.6% byweight was obtained.

Example 18 The procedure of Example 17 was repeated with the exceptionthat ptilolite was employed instead of gmelinite. When the the resultingcatalyst was used to crack decane, it gave a conversion of 58.7% byweight.

Example 19 The procedure of Example 17 was repeated with the exceptionthat the aluminosilicate employed was identified as chabazite. Theresulting catalyst gave a conversion of by weight when employed to crackdecane.

Example 20 A synthetic crystalline aluminosilicate, identified asZeolite 13X, was subjected to 12 two-hour treatments at 180-F. with anaqueous solution containing 5% by weight mixture of rare earth chloridesand 2% by weight of ammonium chloride. The aluminosilicate was thentreated with a 10% by weight aqueous solution of ammonium carbonate for4 hours at 180 F. The resulting modified aluminosilicate was then washedwith water until there were no chloride or carbonate ions in theefliuent, dried and then treated for 24 hours at 1200 F. with steam at15 p.s.i.g. to yield a catalyst having a sodium content of 0.65 weightpercent.

The following table shows the cracking data obtained when the catalystwas evaluated for cracking gas oil at 900 F.:

TABLE 12 Cracking data:

Conversion, vol. percent 43.4 LHSV 8 10 R.V.P. gaso., vol. percent 40.9Excess C s, vol. percent 5.8 0 gasoline, vol. percent 38.6 Total C.{s,vol. percent 8.2 Dry gas, wt. percent 3.6 Coke, wt. percent 0.9 H wt.percent 0.02

A advantage:

10 R.V.P., vol. percent +5.1 Excess C s, vol. percent 2.9 0 gasoline,vol. percent +5 .1 Total C s, vol. percent 2.8 Dry gas, wt. percent -1.3Coke, wt. percent -1.12

Example 21 The procedure of Example 20 was repeated with the exceptionthat a 10% by weight aqueous solution of ammonium phosphate was employedinstead of the ammonium carbonate. The resulting catalyst had a sodiumcontent of 0.5 weight percent and the cracking data shown in thefollowing table when used at 900 F C gasoline, vol. percent 33.5

Total C s, vol. percent 9.3 Dry gas, wt. percent 4.7 Coke, wt. percent2.1 H wt. percent 0.02

Example 22 5 parts by weight of the synthetic crystallinealuminosilicate identified as Zeolite 13X was incorporated into 95 partsby weight of a silica-alumina matrix consisting of 94 weight percent ofSiO and 4 weight percent of A1 The resulting composition was thentreated with an aqueous solution containing 1% by weight mixture of rareearth chlorides and 1% by weight of ammonium chloride for 12 contacts of2 hours each. The treated aluminosilicate was then washed with wateruntil there were no chloride ions in the efiluent, dried and treated for24 hours at 1200 F. with steam at 15 p.s.i.g. to yield a catalyst havinga sodium content of 0.07 weight percent.

The following table shows the cracking data obtained when the catalystwas evaluated for cracking gas oil at 900 F.:

TABLE 14 Cracking data:

Conversion, vol. percent 50.5 LHSV 4 1 0 R.V.P. gaso., vol. percent 45.0Excess C s, vol. percent 8.7 0 gasoline, vol. percent 42.7 Total C s,vol. percent 11.0 Dry gas, wt. percent 4.7 Coke, wt. percent 1.6 H wt.percent 0.04

A advantage:

R.V.P., vol. percent +5.1 Excess C s, vol. percent +2.0 C gasoline, vol.percent +5.2 Total C s, vol. percent +2.0 Dry gas, wt. percent 1.4 Coke,wt. percent 1.4

Example 23 The procedure of Example 22 was repeated with the exceptionthat one contact of 24 continuous hours was employed instead of 12two-hour contacts. The sodium content of the resulting aluminosilicatewas 0.1 weight percent and it had the cracking data shown in thefollowing table when employed at a temperature of 900 F.:

TABLE 15 Cracking data:

Conversion, vol. percent 51.5 LHSV 4 10 R.V.P. gaso., vol. percent 45.8Excess C s, vol. percent 9.4 C gasoline, vol. percent 43.5 Total C s,vol. percent 11.7 Dry gas, wt. percent 4.7 Coke, wt. percent 1.5 H wt.percent 0.03

A advantage:

10 R.V.P., vol. percent +5.3 Excess C s, vol. percent -1.6 C gasoline,vol. percent +5.3 Total C s, vol. percent 1.6 Dry gas, wt. percent 1.6Coke, wt. percent c 1.7

20 Example 24 25 parts by weight of a crystalline aluminisolicateidentified as Zeolite 13X was dispersed in 75 parts by weight of silicondioxide and the resulting composition treated for 24 continuous hourswith an aqueous solution consisting of 1% by weight mixture of rareearth chlorides and 1% by weight of ammonium chloride. Thealuminosilicate was then washed with water, until there were no chlorideions in the effiuent, dried and then treated for 24 hours at atemperature of 1200 F. with steam at 15 p.s.i.g. to yield a catalysthaving the cracking data shown in the following table when evaluated forcracking gas oil at 900 F.:

TABLE 16 Cracking data:

Conversion, vol. percent 61.5 LHSV 4 10 R.V.P. gaso., vol. percent 53.8Excess C s, vol. percent 9.8 C gasoline, vol. percent 50.9 Total C s,vol. percent 12.6 Dry gas, wt. percent 5.9 Coke, wt. percent 3.0 H wt.percent 0.02

A advantage:

10 R.V.P., vol. percent +8.2 Excess C s, vol. percent 4.6 C gasoline,vol. percent +7.5 Total C s, vol. percent 3.9 Dry gas, wt. percent +1.9Coke, wt. percent 1.7

Example 25 The procedure of Example 24 was repeated with the exceptionthat the composition was first treated with a 2% by weight aqueoussolution of a mixture of rare earth chlorides for 16 continuous hours,washed and then treated with a 1% by weight aqueous solution of ammoniumchloride for 24 continuous hours. The resulting catalyst contained 4.35weight percent rare earths, determined as rare earth oxide, and had thecracking data shown in the following table:

TABLE 17 Cracking data:

Conversion, vol. percent 48.4 LHSV 4 10 R.V.P. gaso., vol. percent 44.6Excess C s, vol. percent 6.5 C gasoline, vol, percent 42.1 Total C s,vol. percent 9.0 Dry gas, wt. percent 4.6 Coke, wt. percent 1.3 H wt.percent 0.02

A advantage:

10 R.V.P., vol. percent +5.8 Excess C s, vol. percent 3.5 C gasoline,vol. percent +5.6 Total C s, vol. percent +3.5 Dry gas, wt. percent 1.1Coke, wt. percent l.4

Example 26 10 parts by weight of a synthetic crystalline aluminosilicateidentified as Zeolite 13X was dispersed into parts by weight of a silicaalumina matrix consisting of 93% by Weight SiO and 7% by Weight of A1 0The composition was then treated for one two-hour contact with a 1% byweight aqueous solution of rare earth chlorides, washed and thensubjected to one 24 hour continuous contact with an aqueous solutionconsisting of 2% by Weight of calcium chloride and 1% by weight ofammonium chloride. The aluminosilicate was then washed with water untilthere were no chloride ions in the efiluent, dried and then treated for20 hours at 1225 F. with 1% atmos- 21.- pheric steam to yielda'cat'alyst having a sodium content of 0.1% by Weight, a calcium contentof 2.2% by weight, and a rare earth content,determ'inedasrare earthoxides, of 5.1% by'weighta i The followingtable-shows cracking dataobtained when the catalyst was evaluated for cracking gas oil at900 F.:

TA-BLE' 18' Cracking'dataw- W r Conversion, vol. percent 51.1 LHSV 4 i'10-R.V.P. gaso.,-vol. percent 44.5 Excess C s, vol." percent 8.8 Cgasoline -vol. percent 42.4 Total s, vol. percent 10.9 -Drygas,-wt.-percent- 4.8 Coke, 'wtapercent a 2.2

A advantage: -R.v.P-,vo .-,p. c nt -.--4 ---.-4----- Excess C s, vol.percent +2.1 -C5+gasoline, vol. percent +4.4. Total C s, vol. percent2.3 Dry gas, wt. percent .1.4

Coke, wt. percent 0u4 Example 27 The procedure of Example 26 wasrepeated with the exception that. 2 two-hour contacts of a rare earthchloride mixture were employed instead of 1. two-hour contact. Theresulting aluminosilicate had a. sodium content. of 0 y weight, a alc umc n (if by Weight, and a rare earth content, determined as rare earthoxides, of 7.7% by weight. 4 r w The following table shows the crackingdata of the catalyst when evaluated for cracking gas oil at 900 F.:

Crackingdatazh u i Conversion, -vol. percent 53. LHSV Ql*0"R.V.P."gaso., .vol. percent L; 7 Excess C s, vohpercent C gasoline,vol. percent 4 Total C s, vol. percent 1 Dry gas, wt. percent 3; "*Coke,wt'percent 7 a ant .0 R.V.P. 1. p r nt.

, Exces s C s, vol. percent,

4 5+ cl n lp n ,.Tota1. .4? V L-p r nt.

.- ys rw Pe c t Coke, wt. percent "Eaapzzzsff; U

v10 .parts by' of a synthetic crystalline aluminosilicate identified asZeolite 13X was dispersed in 90 parts by weight of a silica alumina.matrix consisting of 93% ana st- ,TABLE 2 0 Cracking data:

Conversion, vol. percent 54.8' LHSV 4 10 R.V.P. gaso., vol. percent 48.3

' Excess C s, vol. percent 9.1 C gasoline, vol. percent 45.8

Total C s, vol. percent 11.5 "Dry gas, Wt. percent 4.8 Coke, wt. percent2.5 H wt. percent -a- 0.03

A advantage: p V, 7 p

' 10 R. V. P., vol., percent +6.1 Excess C s, vol. percent +2.9 Cgasoline, vol. percent L +6.0 Total C s,'vol.'percent 2.7 Dr-y gas, wt.percent 1.9 Coke,-wt.' percent 1.1

- "Example 29 With a" 1% by Weight aqueous solution of ammonium sul- SiOand 7% A1 0 The composition was then treated for 24 continuous hourswith a 1% by weight solution of a mixture of rare earth chloride and a1% 'by weight solution of ammonium .chloride. .The aluminosilicate' wastheir washedwith-water until there wasno'chloride ions in the efiluent,.dried. and then treated for 30* hours at 1 cracking dataof the fate forthree 16 hour contacts and then'for 9 two-hour contacts with the samesolution. The aluminosilicate' was then Washed with water until therewere no chloride or sulfate ions in the efliuent, dried and then treatedfor 30 1 hours at 1200" F. with steam at a pressure of 15 p.s.i.g.

toyield a catalyst having a sodium content of 0.17% by weight anda -rareearths content,- determined'fas rare earth oxides, of 4.5 %by weight.

The following table shows the'cracking data of the catalyst whenevaluated for cracking gas oil' at 900 F.:

- TABLE 21 Crackingdataz V 7 7 a Conversiomvol, percent 57.4 LHSV 4 10R.V.P. gas0., vol. percent 48.3 Excess C s, vol. percent Q 11.1 Cgasoline, vol. percent 46.2 Total C s, vol. percent 13.3 'Dry gas, wt.percent 6.0 Coke, wt. percent 2.5 H wt. percent 0.02

I A advantage:

: 'Cokeywt. percent 1.6

- Example'30 10 parts by-Weight of a crystalline. synthetic alumino-.silicate identified .asZeolite. 13X was. dispersed into parts ofa-silica alumina matrixand the composition was treated with an aqueoussolution consisting of 1% .by weight of .didyniumchloride. and 1%. .byweightof am: monium chloride. for 24 continuous hours. The,aluminosilicatewas then washedwith water until .there Wereno chlorideions in the efiluent, dried and then treated for24 hoursatv1200.9..F.,.with steam at. a pressure of-15 p.s.i.g. to yield a catalysthaving 8.77%- by Weight of rare earths, determined as rare earth oxides.

The following table shows the cracking data of the catalyst whenevaluated for cracking gas oil at 900 F.:

TABLE 22 Cracking data:

Conversion, vol. percent 63.1 LHSV 4 10 R.V.P gaso., vol. percent 52.7Excess C s, vol. percent 11.8 C gasoline, vol. percent n 50.1 Total C s,vol. percent 14.4 Dry gas, wt. percent 7.1 Coke, wt. percent 3.3 H wt.percent 0.18

A advantage:

1O R.V.P., vol. percent +6.2 Excess C s, vol. percent 3.2 gasoline, vol.percent +5.9 Total C s, vol. percent 2.6 Dry gas, wt. percent 1.1 Coke,wt. percent -1.8

Example 31 The procedure of Example 30 was repeated with the exceptionthat a 2% by weight solution of didynium chloride was employed for 16continuous hours and then a 1% by weight solution of ammonium chloridewas employed for 24 continuous hours. The cracking data of the resultingcatalyst is shown in the following table:

TABLE 23 Cracking data:

Conversion, vol. percent 58.6 LHSV 4 R.V.P. gaso., vol. percent 50.8Excess C s, vol. percent 11.1

C gasoline, vol. percent 48.6

Total C s, vol. percent 13.3 Dry gas, wt. percent 5.6 Coke, wt. percent2.1 H wt. percent 0.04

A advantage:

10 R.V.P., vol. percent +6.7 Excess C s, vol. percent 2.1 C gasoline,vol. percent +6.7 Total C s, vol. percent -2.2 Dry gas, wt. percent 1.8Coke, wt. percent 2.1

Example 32 25 parts by weight of a synthetic crystalline aluminosilicateidentified as Zeolite 13X was dispersed in 75 parts of a silica aluminamatrix and the resulting composition treated with a 2% by weightsolution of calcium chloride for 8 continuous hours, followed bytreatment with an aqueous solution consisting of 2% by weight of calciumchloride and 0.5% by weight of ammonium chloride for 16 continuous hoursand then treated with a 2% by weight aqueous solution of rare earthchlorides for 2 contacts each of 2 hours. The aluminosilicate was thenwashed with Water until there was no chloride ions in the effluent,dried and then treated for 20 hours at 1225 F. with 1% atmospheric steamto yield a catalyst having calcium content of 2.15% by weight and a rareearths content, determined as rare earth oxides, of 7.2% by weight.

The following table shows the cracking data of the catalyst whenevaluated for cracking gas oil at 900 F.:

24 TABLE 24 Cracking data:

Conversion, vol. percent 57.3 LHSV 4 10 R.V.P. gaso., vol. percent 46.1Excess C s, vol. percent 11.3 C gasoline, vol. percent 43.3 Total C s,vol. percent 14.1 Dry gas, wt. percent 6.1 Coke, wt. percent 4.0 H wt.percent 0.03 Aadvantage:

10 R.V.P., vol. percent +2.7 Excess C s, vol. percent 1.6 C gasoline,vol. percent +2.0 Total C s, vol. percent -1.0 Dry gas, wt. percent +0.6Coke, wt. percent 0.1

Example 33 25 parts by weight of a synthetic crystalline aluminosilicateidentified as Zeolite 13X was dispersed in 75 parts by weight of asilica alumina matrix and the resulting composition treated with anaqueous solution consisting of 2% by Weight mixture of rare earthchlorides and 0.5% by weight of acetic acid for 12 contacts each beingtwo hours in duration. The aluminosilicate was then washed with wateruntil there were no chloride or acetate ions in the effluent, dried andthen treated for 20 hours at 1225 F. with a atmospheric steam to yield acatalyst having a rare earths content, determined as rare earth oxides,of 3.17.

The following table shows the cracking data of the catalyst whenevaluated for cracking gas oil at 900 F.:

TABLE 25 Cracking data:

Conversion, vol. percent 43.0 LHSV 4 10 R.V.P. gaso., vol. percent 34.3Excess C s, vol. percent 9.6 C gasoline, vol. percent 32.6 Total C s,vol. percent 11.1 Dry gas, wt. percent 5.1 Coke, wt. percent 2.4 H wt.percent 0.02

Example 34 25 parts by Weight of a synthetic crystalline aluminosilicateidentified as Zeolite 13X was dispersed into 75 parts of a silicaalumina matrix and the resulting composition treated with an aqueoussolution consisting of 2% by weight of calcium chloride and 1% by weightof ammonium chloride for 2 treatments of 2 hours each. Thealuminosilicate was then washed with water until there were no chlorideions in the effluent, dried and then treated for 20 hours at 1225 F.with 100 atmospheric steam to yield a catalyst having a sodium contentof 0.69 and a calcium content of 3.44.

The following table shows the cracking data of the catalyst whenevaluated for cracking gas oil at 900 F.:

TABLE 26 Cracking data:

Conversion, vol. percent 48.3 LHSV 4 10 R.V.P. gaso., vol. percent 46.6Excess C s, vol. percent 4.0 C gasoline, vol. percent 43.2 Total C s,vol. percent 7.4 Dry gas, wt. percent 4.1 Coke, wt. percent 1.5 H wt.percent 0.02

A advantage:

10 R.V.P., vol. percentue... +7.9 Excess C s, vol. percent -6.0 Cgasoline, vol. 'percent +6.8 Total C s, vol. percent 4.0 Dry gas, wt.percent-HI -1.6

Example 35' i The procedure of Example 34 was repeated with theexception that 12 two-hour contacts of treating solution were employedinstead of 2 two hour contacts. The sodiurn content oftheresultingaluminosilicate was 0.17%

by Weight and the calcium contentwas 3.24% by weight.

The cracking data of the catalyst are shown in the following table: a

:TABLE 27 Cracking data:

Excess C s, yol. percent parts by weight of-a synthetic crystallinealumino silicate identified as Zeolite 13X was dispersedinto 90 parts byweight of a silica alumina matrix andtheresulting'cor'n'positionwas'treated with a 2% aqueous solution oflanthanum chloride forfone continuous 16 hour contact andthentreatedwith a 1% solutionfof ammonium chloride 'for" 24 continuoushours. Y .The 'alumino silicate was. then Washed with 'water untiltherewas no chloride ions in'the'efiiue'm; dried and then treated for 24hours at .1200F.with s'te'arnat'IS p.s.i.g. to yieldfacatalyst having'alamhanumoxidecontent of 5.92. f

The followingtable' showswhe cracking data of the catalyst whenevaluated for cracking gas oil at 900 F. i

10 parts by weight of a rare earth synthetic aluminosilicate prepared byreacting Zeolite 13X with a rare earth chloride solution was dispersedin a silica alumina matrix and the resulting composition was treatedwith a solution consisting of. 2% by weight of calciumchloride and-1'%26 by weight of ammonium chloride for 24 continuoushour's. Thealuminosilicate was then washed with water until there were no chlorideions in the eflluent; dried and then treated for 20 hours-at 1-22 5 F.with 100% atmospheric 5 steam to yield a catalyst-having a sodiumcontent of 0.12 weight percent, calcium content of 2.5 weight percent,and'a rare earths content, determined as rare earth oxides, of 2:4weight-percent.----

t v V The following table shows the cracking data of the 10 catalystwhen evaluatedfor cracking gasoil at900 F.:

TABLE29;

cratzlcingdata: I Conversio vol. percent 46.2 *LH v. J 4 10'R.V.P.gaso.,vo1.percent 37.1 Excess Cis, vol. percent 9.3 C gasoline, vollpercent35.4 Total C s, vol. percent 11.0

Dry gas, wt. percent .1. 5.4 1' Coke,wt. percent 3.0 1 H wt.. percent 0.03

' "Example 3 8 .j p p 1 The proced of Example 3-7 was repeated with theexcepti thatthe treating solution was'a 1% by weight solutio ammoniumchloride'instead of asolution of calcium oniurn chlorides. The resultingcatalyst s n ned 9.11%. byweight Sodium and 2.05% by weight rare earthsand had the cracking data li ted i th -f n n lea. 7

p Example 39 5 10 p arts by weight of a cerium aluminosilicate. preparedby reacting an aluminosilicate identified as Zeolite.1 3X with asolution of cerium chloride was dispersed into. a silica alumina matrixand the resulting compos'ition was treated withfa 1% by weight solutionof ammonium chloride for 24coritinuous hours. The aluminosilicate wasthen washed with Water until there were no chloride ions in theefiluent, dried and then treated for 24iho'1irs' at 1200"...13. withsteamat 15'p.'s'.i.g. toyield a catalyst having a cerium contentof 2. 2%byweight. V

'i.The..following tableshows' the cracking data for the catalyst whenevaluated-for cracking "gasoil" at 900 F.:

2? TABLE 3lContinued A advantage:

10 R.S.V., vol. percent +4.0

Excess C s, vol. percent -1.8

C gasoline, vol. percent +4.0

Total C s, vol. percent +1.9

Dry gas, wt. percent 1.3

Coke, wt. percent 0.6

Example 40 The procedure of Example 39 was repeated with the exceptionthat the cerium aluminosilicate dispersed in the matrix was firsttreated with a 2% by weight solution of cerium chloride for 16 hours andthen with a 1% by weight solution of ammonium chloride for 24 continuoushours. The resulting catalyst contained 6.6% by weight of cerium and itscracking data is shown in the following table when evaluated forcracking gas oil at 900 F.:

TABLE 32 Cracking data:

Conversion, vol. percent 54.3 LHSV 4 1O R.S.V. gas., vol. percent 45.4Excess C s, vol. percent 10.7 C gasoline, vol. percent 43.5 Total C s,vol. percent 12.6 Dry gas, wt. percent 5.4 Coke, wt. percent 3.0 H wt.percent 0.02 A advantage:

R.S.V., vol. percent +3.4 Excess C s, vol. percent 1.2 C gasoline, vol.percent +3.7 Total C s, vol. percent 1.6 Dry gas, wt. percent 1.3 Coke,wt. percent 0.6

Example 41 10 parts by weight of a lanthanum aluminosilicate prepared byreacting Zeolite 13X with a 5% by weight lanthanum chloride at 180 F.for one two-hour contact was dispersed in a silica alumina matrix andthe resulting composition treated with a 1% by weight solution ofammonium chloride for 24 continuous hours. The aluminosilicate was thenwashed with water, dried and then treated for 24 hours at 1200 F. withsteam at 15 p.s.i.g. to yield a catalyst having a rare earth content of0.52% by weight, determined as rare earth oxides.

Example 42 The procedure of Example 41 was repeated with the exceptionthat the aluminosilicate in the matrix was first treated with a 2% byweight solution of lanthanum chloride for 16 hours prior to thetreatment with the 1% by weight solution of ammonium chloride for 24hours. The resulting catalyst had a lanthanum content of 6.1% by weightand its cracking data is shown in the following table when evaluated forcracking gas oil at 900 F TABLE 33 Cracking data:

Conversion, vol. percent 60.5 LHSV 4 10 R.V.P. gaso., vol. percent 51.5Excess C s, vol. percent 12.2 C gasoline, vol. percent 49.1 Total C s,vol. percent 14.5 Dry gas, wt. percent 6.0 Coke, wt. percent 2.0 H wt.percent 0.02 A advantage:

10 R.V.P., vol. percent +6.5 Excess C s, vol. percent 1. 8 C gasoline,vol. percent +6.1 Total C s, vol. percent -1.5 Dry gas, wt. percent -l.7Coke, wt. percent 2.6

28 Example 43 The procedure of Example 38 was repeated with theexception that the matrix was SiO instead of a silica alumina matrix.The resulting catalyst had a rare earth content of 3.7% by weight.

Example 44 The procedure of Example 39 was repeated with the exceptionthat the matrix was SiO instead of silica alumina. The resultingcatalyst had a rare earth content of 5.3% by weight.

Example 45 The procedure of Example 41 was repeated with the exceptionthat the matrix was SiO instead of silica alumina. The resultingaluminosilicate had a rare earth content of 3.7% by weight.

Example 46 The procedure of Example 42 was repeated with the exceptionthat the matrix was SiO instead of silica alumina. The resultingcatalyst had a rare earth content of 9.1% by weight.

Example 47 25 parts by weight of a synthetic crystalline calciumaluminosilicate was dispersed into 75 parts by weight of a silicaalumina matrix and the resulting composition treated with a 2% aqueoussolution of rare earth chlorides for 16 continuous hours and then with a1% by weight solution of ammonium chloride for 24 continuous hours. Thealuminosilicate was washed with water until the effluent contained nochloride ions and then treated for 24 hours at 1200 F. with steam at 15p.s.i.g. to yield a catalyst having a rare earth content, determined asrare earth oxides, of 4.97% by weight.

The following table shows the cracking data for the catalyst whenevaluated for cracking gas oil at 900 F.:

TABLE 34 Cracking data:

Conversion, vol. percent 51.5 LHSV 4 10 R.V.P. gaso., vol. percent 49.3Excess C s, vol. percent 8.0 C gasoline, vol. percent 47.0 Total C s,vol. percent 10.3 Dry gas, wt. percent 6.1 Coke, wt. percent 2.1 H wt.percent 0.01 A advantage:

10 R.V.P., vol. percent +8.9 Excess C s, vol. percent -3.0 C gasoline,vol. percent +9.0 Total C s, vol. percent 3.0 Dry gas, wt. percent O.2Coke, wt. percent 1.0

Example 48 10 parts by weight of a crystalline aluminosilicateidentified as Zeolite 13X was dispersed into parts by weight of a silicalanthanum matrix containing 98.5% by weight of SiO and 1.5% by weight oflanthanum oxides. The resulting composition was treated with a 2%aqueous solution of lanthanum chloride for 16 continuous hours and thenwith a 1% solution of ammonium chlo ride for 24 continuous hours. Thealuminosilicate was then washed with water until there were no chlorideions in the efiluent, dried and then treated for 24 hours at 1200 F.with steam at a pressure of 15 p.s.i.g. to yield a catalyst having arare earth content of 9.32% by weight.

parts by weight of a silica rare earth oxide matrix consisting of 97% byweight of SiO; and 3% by weight of 29 rare earth oxides. The resultingcompositon was treated with an aqueous solution consisting of 2% byweight of a mixture of rare earth chlorides for 16 hours and then with a1% by weight solution of ammonium chloride for 24 continuous hours. Theresulting aluminosilicate was washed with water until the efliuentcontained no chloride ions, dried and then treated for 24 hours at 1200F. at 15 p.s.i.g. with steam to yield a catalyst having a rare earthcontent of 7.8% by weight, determined as rare earth oxides.

Example 50 r parts by weight of a synthetic crystalline aluminosilicateidentified as Zeolite 13X was dispersed into 90 parts by weight of asilica didynium matrix consisting of 97% by weight SiO and 3% by weightdidynium oxides. The resulting composition was then treated for 16continuous hours with an aqueous solution consisting of 2% by weight oflanthanum chloride and then for 24 continuous hours with 1% by weightaqueous solution of ammonium chloride. The aluminosilicate was thenwashed with water until the efliuent contained no chloride ions, driedand then treated for 24 hours at 1200 F. with steam at p.s.i.g. to yielda catalyst having a rare earth content of 7.79% by weight, determined asrare earth oxides.

The resulting catalyst had the cracking data shown in the followingtable when evaluated for cracking gas oil at 900 F.:

TABLE 35 Cracking data:

Conversion, vol. percent 53.3 LHSV 4 10-R.V.P. gaso., vol. percent 47.8Excess C s, vol. percent 7.8 C gasoline,vol. percent h 45.3 Total C s,vol. percent 10.3 Dry gas, wt. percent 5.1 Coke, wt. percent 2.0 H wt.percent 0.05

A advantage: 7

10 R.V.P., vol. percent +6.4 Excess C s, vol. percent 5.4 05+ gasoline,vol. percent +6.2

TotalC s, vol; percent -5.1

' Dry gas, 'wt. percent l.4 Coke, wt. percent l.4

.. Example'51 The procedure of Example 50 was repeated with theexception that a 2% by weight aqueous solution of didynium chloride wasemployed instead of the lanthanum chloride. The resulting catalyst had asodium content of 0.5% by weight and a rare earth content of 11.2% byweight, and the cracking data shown in the following table:

TABLE 36 Cracking data:

Conversion, vol. percent 48.1 LHSV 4 10 R.V.P. gaso., vol. percent 43.4Excess Cis, vol. percent 6.6 C gasoline, vol. percent -44.0 Total C s,vol. percent 9.1 Dry gas, wt. percent 4.7 Coke, wt. percent 1.6 H wt.percent 0.08

A advantage: I

10 R.V.P., vol. percent +4.9 Excess Cgs, vol. percent --3.4 C+-gasoline,vol. percent +4.8 Total C s,'vol. percent Q. --3.2 Dry gas,wt. percent r r -1.0 Coke, wt. percent +1.0

Example 52 10 parts by weight of a synthetic crystalline aluminosilicateidentified as Zeolite 13X was dispersed in parts by weight of a silicaalumina lanthanum matrix consisting of 91% by weight SiO 3% by weight A10 and 6% by weight of lanthanum oxides. The resulting composition wastreated with a 1% by weight aqueous solution of lanthanum chloride andthen with a 1% by weight solution of ammonium chloride, each treatmentbeing for 24 continuous hours. The aluminosilicate was then washed withwater until the efiiuent contained ,no chloride ions, dried and thentreated for 24 hours at 1200 F. with steam at 15 p.s.i.g. to yield acatalyst having a sodium content of 0.15% by weight, and a rare earthcontent of 11.5% "by weight, determined as rare earth oxides. Thecracking data' of the resulting catalyst are shown in thefollowingtable, when the catalyst was evaluated for cracking gas oil at 900 F l I1 TABLE 37 Cracking data:

Conversion, vol. percent 54.0 LHSV 4 10 R.V.P. gaso., vol. percent a49.8 Excess C s,vo1. percent 7.5 C gasoline, vol. percent 46.9 Total Cs, vol. percent 10.4 Dry gas, wt. percent, 4.8 Coke, wt. percent 1.8 Hwt. percent 0.01

A advantage:

10 R.V.P., vol. percent +8.0 Excess C s, vol. percent 5.9 C gasoline,vol. percent +7.4 Total C s, vol. percent 5.2 .Dry' gas, 'wt. percent-2.7

Coke, wt. percent -2; 2.6

. Example 53 v 10 parts by weight of a crystalline aluminosilicateidentified as Zeolite Y was dispersed into 90 parts by weight of asilica alumina matrix and the resulting composition was treated for 16continuous hours withan aqueous solution comprising a 2% by weightmixture of rare earth chlorides and then for 24 continuous hours with a1% by weight aqueous ammonium chloride solution.- The aluminosilicatewas then washed withwater until the efiiuent contained no chloride ions,dried and then treated for 24 hours at 1200 F. with steam at 15 p.s.i.g.to yield a catalyst having a rare earthcontent of 3.35 weight percent. fv V p The "crackingdata' of the resulting catalyst is shown in the"renewin table when evaluated for'cracking gas oilat 900"F.':' I

A ABLE 38 Coke, wt. percent +2.2

31 Example 54 The procedure of Example 53 was repeated with theexception that a 2% by weight aqueous solution of lanthanum chloride wasemployed instead of the rare earth chloride solution. The resultingcatalyst had a lanthanum content of 3.9 weight percent determined aslanthanum oxide.

The cracking data of the resulting catalyst is shown in the followingtable:

TABLE 39 Cracking data:

Conversion, vol. percent 61.8 LHSV 4 10 R.V.P. gaso., vol. percent 54.0Excess C s, vol. percent 11.1 C gasoline, vol. percent 51.5 Total C s,vol. percent 13.7 Dry gas, wt. percent 5.8 Coke, wt. percent 2.0 H wt.percent 0.02

A advantage:

R.V.P., vol. percent +8.2 Excess C s, vol. percent 3.3 C gasoline, vol.percent +8.0 Total C s, vol. percent 2.8 Dry gas, wt. percent 2.2 Coke,wt. percent 2.8

Examples 55-67 illustrate the use of clays which have been treated withcaustic admixture with a source of silica, such as sand, silica gel orsodium silicate, calcined at temperatures ranging from 350 F. to 1600F., crushed, dispersed in water and digested.

Example 55 10% by weight of a McNamee clay which had been caustictreated was dispersed in 90 parts by weight of a silica alumina matrix.The resulting composition was treated with a 2% aqueous solution oflanthanum chloride for 16 continuous hours and then with a 1% by weightsolution of ammonium chloride for 24 continuous hours. The resultingaluminosilicate was washed with water until the effiuent contained nochloride ions, dried and then treated for 24 hours at 1200 F. with steamat p.s.i.g. to yield a catalyst having a lanthanum content of 5.15,determined as lanthanum oxide.

The following table shows the cracking data of the catalyst whenevaluated for cracking gas oil at 900 F.:

TABLE 40 Cracking data:

Conversion, vol. percent 54.2 LHSV 4 10 R.V.P. gaso., vol. percent 48.8Excess C s, vol. percent 9.8 C gasoline, vol. percent 46.6 Total C s,vol. percent 11.9 Dry gas, wt. percent 4.8 Coke, wt. percent 1.4 H Wt.percent 0.04

A advantage:

10 R.V.P., vol. percent '+6.9 Excess C s, vol. percent 2.0 C gasoline,vol. percent +7.0 Total C s, vol. percent 2.1 Dry gas, wt. percent +1.9Coke, wt. percent 2.1

Example 56 The process of Example 55 was repeated with the exceptionthat the matrix was a silica gel instead of the silica alumina employed.The resulting aluminosilicate catalyst had a lanthanum oxide content of6.06% by weight.

32 Example 57 10 parts by weight of a caustic treated McNamee clay wasdispersed into a silica lanthanum matrix consisting of 97 parts byweight of Si0 and 3 parts by weight of lanthanum oxide. The resultingcomposition was subjected to a 24 hour continuous treatment with anaqueous solution consisting of 1% by weight lanthanum chloride and 1% byweight ammonium chloride. The aluminosilicate was then washed with wateruntil the eflluent contained no chloride ions, dried and then treatedfor 24 hours at 1200 F. with steam at 15 p.s.i.g. to yield a catalysthaving a lanthanum content of 10.2% by weight, determined as lanthanumoxide.

Example 58 25 parts by weight of caustic treated McNamee clay wasdispersed in 75 parts by weight of a silica lanthanum matrix consistingof 97% by Weight of silica and 3% by weight of lanthanum oxide. Theresulting composition was then treated with a 2% solution of didyniumchloride for 16 continuous hours and then with a 1% solution of ammoniumchloride for 24 hours. The resulting aluminosilicate was then washedwith water until the efiluent contained no chloride ions, dried and thentreated for 24 hours at 1200 F. with steam at 15 p.s.i.g. to yield acatalyst having a rare earth content of 9.45% by weight, determined asrare earth oxides.

The following table shows the cracking data of the catalyst whenevaluated for cracking gas oil at 900 F.:

TABLE 41 Cracking data:

Conversion, vol. percent 61.6 LHSV 4 l0 R.V.P. gaso., vol. percent 53.3Excess C s, vol. percent 10.8 C gasoline, vol. percent 50.7 Total C s,vol. percent 13.4 Dry gas, wt. percent 5.9 Coke, wt. percent 2.5 H wt.percent 0.11

A advantage:

10 R.V.P., vol. percent +7.6 Excess C s, vol. percent 3.6 C gasoline,vol. percent +7.2 Total C s, vol. percent 3.1 Dry gas, wt. percent +2.0Coke, wt. percent 2.3

Example 59 10 parts by weight of a caustic treated bentonite clay wasdispersed in parts of a silica alumina matrix and the resultingcomposition was subjected to a 16 hour continuous treatment with anaqueous solution consisting of 2% by weight of lanthanum chloride andthen with a 1% aqueous solution of ammonium chloride for 24 continuoushours. The resulting aluminosilicate was then washed with water untilthe efiiuent contained no chloride ions, dried and then treated for 24hours at 1200 F. to obtain a catalyst having a lanthanum content of5.66% by weight.

The following table shows the cracking data of the catalyst whenevaluated for cracking gas oil at 900 F.:

TABLE 42 Cracking data:

Conversion, vol. percent 51.1 LHSV 4 10 R.V.P. gaso., vol. percent 44.6Excess C s, vol. percent 8.7 C gasoline, vol. percent 42.3 Total C s,vol. percent 10.9 Dry gas, wt. percent 5.4 Coke, wt. percent 1.5 H wt.percent 0.11

. 33 TABLE 42Continued A advantage:

10 R.V.P., vol. percent +4.5 Excess C s, vol. percent +2.3 gasoline +4.3Total C s, vol. percent +2.3 Dry gas, wt. percent +0.8 Coke, wt. percent+1.6

' Example 60 parts by weight of halloysite clay which had been caustictreated was dispersed in 90 parts by weight of a silica alumina matrixand the resulting composition treated with a 2% by weight aqueoussolution of a mixture of rare earth chlorides for 16 hours and then witha 1% by weight aqueous solution of ammonium chloride for 24 continuoushours. The aluminosilicate was then washed with water until the effluentcontained no chloride ions, dried and then treated for 24 hours at 1200F. with steam at a pressure of p.s.i.g. to yield a catalyst having arare earth content of 6.08.

The following table shows the cracking data of the catalyst whenevaluated for cracking gas oil at 900 F.:

TABLE 43 Cracking data:

Conversion, vol. percent 57.6 LHSV 4 10 R.V.P. gaso., vol. percent 50.6Excess C s, vol. percent 10.9 C gasoline, vol. percent 48.3 Total C s,vol. percent 13.4 Dry gas, wt. percent 5.3 Coke, wt. percent 1.7 H wt.percent 0.03 A advantage:

10 R.V.P., vol. percent +7.0 Excess C s, vol. percent +2.1 C gasoline,vol. percent +6.8 Total C s, vol. percent +1.7 Dry gas, wt. percent +2.0Coke, wt. percent 2.5

Example 61 The procedure of Example 60 was repeated with the exceptionthat a 2% by Weight aqueous solution of lanthanum chloride was employedinstead of the rare earth chloride solution. The resulting catalyst hada lanthanum content of 6.82% by Weight and the cracking data shown inthe following table:

TABLE 44 Cracking data:

Conversion, vol. percent 58.4 LHSV 4 10 R.V.P. gaso., vol. percent 49.3Excess C s, vol. percent 11.3 C gasoline, vol. percent 47.0 Total C s,vol. percent 13.6 Dry gas, wt. percent 6.3 Coke, wt. percent 2.0 H wt.percent 0.03 A advantage:

10 R.V.P., vol. percent +5.3 Excess C s, vol. percent +1.9 C gasoline,vol. percent +5.2 Total C s, vol. percent +1.8 Dry gas, wt. percent +1.1Coke, wt. percent 2.3

Example 62 25 parts by weight of a caustic treated Dixie clay wasdispersed into a silica alumina matrix and the composition was treatedwith an aqueous solution consisting of 1% by weight of a mixture of rareearth chlorides and 1% by weight ammonium chloride for 24 continuoushours. The aluminosilicate was then washed with water until the efiluentcontained no chloride ions, dried and then treated 34 for 20 hours at1225 F. with atmospheric steam to yield a catalyst having a sodiumcontent of 0.56% by weight and a rare earth content of 8.2% by weight,determined as rare earth oxides.

The following table shows the cracking data of the catalyst whenevaluated for cracking gas oil at 900 F.:

TABLE 45 Cracking data:

Conversion, vol. percent Q 46.2 LHSV 4 10 R.V.P. gaso., vol. percent40.0 Excess C s, vol. percent 7.3 C gasoline, vol. percent 37.7 Total Cs, vol. percent 9.6 Dry gas, wt. percent 4.7 Coke, wt. percent 2.6 H wt.percent 0.22

A advantage:

10 R.V.P., vol. percent +2.5 Excess C s, vol. percent +2.2 C gasoline,vol. percent +2.6 Total C s, vol. percent"; +2.2 Dry gas, wt. percent+0.7 Coke, wt. percent +0.2

Example 63 25 parts by weight of a caustic treated Dixie clay wasdispersed into a silica alumina matrix and the resulting composition wassubjected to 4 two-hour treatments with a 2% aqueous solution of calciumchloride and then to 8 two-hour treatments with a solution consisting of2% by weight of calcium chloride and 1% by weight of ammonium chloride.The resulting aluminosilicate was then washed with water until theefiluent contained no chloride ions, dried and then treated for 20 hoursat 1225 F. with 100% atmospheric steam to yield a catalyst having acalcium content of 3.88% by weight.

Example 64 McNamee clay, an aluminosilicate which had been caustictreated, was subjected to treatment with an aqueous solution consistingof 5% by weight of a mixture of rare earth chlorides and 2% by weightammonium chloride. The aluminosilicate was then washed with water untilthe eflluent contained no chloride ions and treated for 20 hours at 1225F. with steam at atmospheric pressure. The resulting aluminosilicate wasevaluated for cracking gas oil at 900 F. and gave the following results:

TABLE 46 Cracking data:

Conversion, vol. percent 57.2 LHSV 16 10 R.V.P. gaso., vol. percent 49.9Excess C s, vol. percent 9.5 C gasoline, vol. percent 47.4 Total C s,vol. percent 12.0 Dry gas, wt. percent 5.6 Coke, wt. percent 2.8 H wt.percent 0.05

A advantage:

10 R.V.P., vol. percent +6.5 Excess C s, vol. percent +3.2 C gasoline,vol. percent +6.2 Total C s, vol. percent +3.0 Dry gas, wt. percent +1.6Coke, wt. percent +1.2

A]20s39.85 wt. percent, SiO24:4.9 wt. percent, Fe20a+ 0.35 wt. percent,TiO2+-0.73 wt, percent, CaO-trace, Mg0+ trace, Na2O0.12 wt. percent, K00.10 wt. percent.

35 Example 65 Dixie clay, an aluminosilicate, which had been caustictreated, was treated with an aqueous solution consisting of 5% by weightmixture of rare earth chlorides and 2% by weight of ammonium chloridefor 2 treatments of 24 hours each. The aluminosilicate was then washedwith water until the efiluent contained no chloride ions, dried andtreated with steam for 20 hours at 1225 F. at atmospheric pressure.

The catalytic evaluation of the resulting aluminosilicate is shown inthe following table for cracking gas oil at 900 F.:

TABLE 47 Cracking data:

Conversion, vol. percent 36.9 LHSV 10 10 R.V.P. gaso., vol. percent 36.2Excess C s, vol. percent 2.0 gasoline, vol. percent 33.7 Total C s, vol.percent 4.5 Dry gas, wt. percent 3.5 Coke, wt. percent 1.8 H wt. percent0.15

A advantage:

R.V.P., vol. percent +4.2 Excess C s, vol. percent 5.0 C gasoline, vol.percent +4.0 Total C s, vol. percent 4.8 Dry gas, Wt. percent 0.5 Coke,wt. percent +0.3

Example 66 Bentonite, an aluminosilicate, which had been caustictreated, was treated with an aqueous solution consisting of 5% by weightof a mixture of rare earth chlorides and 2% by weight of ammoniumchloride. The treated aluminosilicate was then washed with water untilthere was no chloride ions in the eflluent, dried and then treated withsteam for 24 hours at 1200" F. at a pressure of p.s.i.g. The resultingaluminosilicate contained 0.2% by weight calcium and possessed excellentcatalytic properties.

Example 67 A silicate solution was prepared by adding 2.28 lbs. of analuminosilicate identified as Zeolite 13X which had been treated withrare earth chlorides and 6.25 lbs. of water. To this was added 13.9 lbs.of sodium silicate and 7.02 lbs. of water, with constant stirring. Anacid solution was then prepared by mixing 28.55 lbs. of water, 2.12 lbs.of Al (SO '18H O, and 0.97 lb. of 96.7 weight percent sulfuric acid. Thesilicate and the acid solution were mixed continuously through a nozzleadding 492 cc. per minute of the silicate solution at 67 F. to 390 cc.per minute of the acid solution at 42 F. to form a hydrosol having a pHof 8.5 which gelled to a firm hydrogel in 1.9 seconds at 63 F. Thehydrogel was then formed into a head in a conventional manner and wastreated with 1% solution of ammonium chloride using 3 overnight and 9two-hour contacts at room temperature. The aluminosilicate was Washedwith water until the effluent contained no chloride ions, dried forhours at 275 F., calcined for 10 hours at 1000 F. and then treated for30 hours at 1200 F. with steam at 15 p.s.i.g. The resulting catalyst hada sodium content of 0.05% by weight and a rare earth content of 7.16% byweight determined as rare earth oxides.

44.51 wt. percent A1203, 38.51 wt. percent S102, 1.27 wt. percent Fe Oa,1.47 wt. percent T102, 0.08 wt. percent CaO, 0.12 wt. percent MgO, 0.08wt. percent NA20 36 The cracking properties of the resulting catalystare shown in the following table when it was evaluated for cracking gasoil at 900 F.:

TABLE 47 Cracking data:

Conversion, vol. percent 62.2 LHSV 4 10 R.V.P. gaso., vol. percent 51.6Excess C s, vol. percent 12.1 0 gasoline, vol. percent 49.2 Total C s,vol. percent 14.5 Dry gas, wt. percent 6.9 Coke, wt. percent 3.2 H wt.percent 0.03 A advantage:

10 R.V.P., vol. percent +5.6 Excess C s, vol. percent 2.4 C gasoline,vol. percent +5.4 Total C s, vol. percent 2.2 Dry gas, wt. percent l.lCoke, wt. percent +1.8

What is claimed is:

1. In the catalytic cracking of a hydrocarbon oil to producehydrocarbons of lower boiling range, the improvement of contacting saidoil under cracking conditions with discrete particles of a catalystcomposition consisting of an inorganic oxide matrix with a crystallinealuminosilicate containing from 0.5 to 1.0 equivalents per gram atom ofaluminum of ions of positive valence consisting of both hydrogen ionsand cations of metals selected from Groups IB through VIII of thePeriodic Table characterized by containing from 0.01 to 0.99 equivalentof hydrogen ion per gram atom of aluminum and from 0.99 to 0.01equivalent per gram atom of aluminum, of cations of metals selected fromGroup 113 through Group VIII of the Periodic Table.

2. In the catalytic cracking of a hydrocarbon oil to producehydrocarbons of lower boiling range, the improvement of contacting saidoil under cracking conditions with discrete particles of a catalystcomposition consisting of an inorganic oxide matrix with a crystallinealuminosilicate containing from 0.8 to 1.0 equivalent per gram atom ofaluminum of ions of positive valence consisting of both hydrogen ionsand cations of metals selected from Groups IB through VIII of thePeriodic Table characterized by containing from 0.01 to 0.99 equivalentof hydrogen ion per gram atom of aluminum and from 0.99 to 0.01equivalent, per gram atom of aluminum, of cations of metals selectedfrom Group IB through Group VIII of the Periodic Table.

3. In the catalytic cracking of hydrocarbon oil to produce hydrocarbonsof lower boiling range, the improvement of contacting said oil undercracking conditions with discrete particles of a catalyst compositionconsisting of an inorganic oxide matrix with a crystallinealuminosilicate containing 1.0 equivalent per gram atom of aluminum ofpositive ions consisting of both hydrogen ions and cations of metalsselected from Group IB through Group VIII of the Periodic Tablecharacterized by containing from 0.01 to 0.99 equivalent of hydrogen ionper gram atom of aluminum and from 0.99 to 0.01 equivalent, per gramatom of aluminum, of cations of metals selected from Group IB throughGroup VIII of the Periodic Table.

4. In the catalytic cracking of a hydrocarbon oil to producehydrocarbons of lower boiling range, the improvement of contacting saidoil under cracking conditions with discrete particles of a catalystcomposition consisting of an inorganic oxide matrix with a crystallinealuminosilicate containing from 0.5 to 1.0 equivalent of ions ofpositive valence per gram atom of aluminum consisting of both hydrogenions and calcium ions characterized by containing from 0.01 to 0.99equivalent 37 of hydrogen ion per gram atom of aluminum and from 0.99 to0.01 equivalent per gram atom of aluminum of calcium ions.

5. In the catalytic cracking of a hydrocarbon oil to producehydrocarbons of lower boiling range, the improvement of contacting saidoil under cracking conditions with discrete particles of a catalystcomposition consisting of an inorganic oxide matrix With a crystallinealuminosilicate containing from 0.8 to 1.0 equivalent of ions ofpositive valence per gram atom of aluminum consisting of both hydrogenions and calcium ions where in the calcium ions comprise from 40 to 85%of the total equivalents of ions of positive valence.

6. In the catalytic cracking of a hydrocarbon oil to producehydrocarbons of lower boiling range, the improvement of contacting saidoil under cracking conditions with discrete particles of a catalystcomposition consisting of an inorganic oxide matrix with a crystallinealuminosilicate containing from 0.5 to 1.0 equivalent of ions ofpositive Valence per gram atom of aluminum consisting of both hydrogenions and magnesium ions wherein the magnesium ions comprise from 40 to85% of the total equivalents of ions of positive valence.

7. In the catalytic cracking of a hydrocarbon oil to producehydrocarbons of lower boiling range, the improvement of contacting saidoil under cracking conditions with discrete particles of a catalystcomposition consisting of an inorganic oxide matrix with a crystallinealuminosilicate containing from 0.8 to 1.0 equivalent of ions ofpositive valence per gram atom of aluminum consisting of both hydrogenions and magnesium ions wherein the magnesium ions comprise 40 to 85% ofthe total equivalents of ions of positive valence.

8. In the catalytic cracking of a hydrocarbon oil to producehydrocarbons of lower boiling range, the improvement of contacting saidoil under cracking conditions with discrete particles of a catalystcomposition consisting of an inorganic oxide matrix with a crystallinealuminosilicate containing 1.0 equivalent per gram atom of aluminum ofions of positive valence consisting of both hydrogen ions and magnesiumions wherein the magnesium ions comprise 40 to 85% of the totalequivalents of ions of positive valence.

'9. The process of claim 2 wherein the aluminosilicate has an atomicratio of silicon to aluminum greater than 1.6.

10. The process of claim 2 wherein the aluminosilicate has an atomicratio of silicon to aluminum greater than 2.7.

11. The process of claim 5 wherein the aluminosilicate has an atomicratio of silicon to aluminum greater than 1.6.

12. The process of claim 5 wherein the aluminosilicate has an atomicratio of silicon to aluminum greater than 2.7.

13. The process of claim 7 wherein the aluminosilicate has an atomicratio of silicon to aluminum greater than 1.6.

14. The process of claim 7 wherein the aluminosilicate has an atomicratio of silicon to aluminum greater than 2.7.

15. A process for converting a hydrocarbon charge which comprisescontacting the same under conversion conditions with a catalystcomprising a crystalline aluminosilicate containing from 0.5 to 1.0equivalent per gram atom of aluminum of ions of positive valenceconsisting of both hydrogen ions and cations of metals selected fromGroup IB through Group VIII of the Periodic Table characterized bycontaining from 0.01 to 0.99 equivalent per gram atom of aluminum, ofhydrogen ion, and from 0.99 to 0.01 equivalent, per gram atom ofaluminum, of cations of metals selected from Group IB through Group VIIIof the Periodic Table, which aluminosilicate is contained in anddistributed throughout a matrix therefor.

16. The process of claim 2 wherein the metal cations are cations oftrivalent metals.

17. The process of claim 2 wherein the metal cations are cations ofdivalent metals.

18. In the catalytic cracking of hydrocarbon oil to produce hydrocarbonsof lower boiling range, the improvement of contacting said oil undercracking conditions with discrete particles of a catalyst compositionconsisting of an inorganic oxide matrix with a crystallinealuminosilicate having no more than 0.25 equivalent per gram atom ofaluminum of alkali metal cations and containing from 0.8 to 1.0equivalent per gram atom of aluminum of ions of positive valenceconsisting of both hydrogen ions and cations of metals selected fromGroup IB through Group VIII of the Periodic Table.

19. In a process for the cracking of a hydrocarbon charge with a solidporous catalyst wherein the products obtained comprise both economicallyvaluable liquid hydrocarbons boiling in the motor fuel range and undesirable by-productsof lesser economic significance, the improvement inselectively evidenced by the production of a substantially greateramount of said valuable liquid hydrocarbons together with concomitantreduction in the yield of undesired by-products from a given hydrocarboncharge, which comprises contacting said charge under cracking conditionswith a catalyst composition comprising an inorganic oxide matrix havingdispersed therein an aluminosilicate having an ordered crystallinestructure and containing from 0.5 to 1.0 equivalent per gram atom ofaluminum of ions of positive valence Wherein the enhanced selectivity ofsaid catalyst composition arises from the fact that the aluminosilicatehas associated therewith both hydrogen ions and cations of metalsselected from Group IB through Group VIII of the Periodic Table.

References Cited in the file of this patent UNITED STATES PATENTS2,369,074 Pitzer Feb. 6, 1945 2.962,435 Fleck et a1. Nov. 29, 19602,971,903 Kimberlin et a1. Feb. 14, 1961 2,971,904 Gladrow et a1. Feb.14, 1961 3,033,778 Frilette May 8, 1962

19. IN A PROCESS FOR THE CRACKING OF A HYDROCARBON CHARGE WITH A SOLIDPOROUS CATALYST WHEREIN THE PRODUCTS OBTAINED COMPRISES BOTHECONOMICALLY VALUABLE LIQUID HYDROCARBONS BOILING IN THE MOTOR FUELRANGE AND UNDESIRABLE BY-PRODUCTS OF LESSER ECONOMIC SIGNIFICANCE, THEIMPROVEMENT IN SELECTIVELY EVIDENCED BY THE PRODUCTION OF ASUBSTANTIALLY GREATER AMOUNT OF SAID VALUABLE LIQUID HYDROCARBONSTOGETHER WITH CONCOMITANT REDUCTION IN THE YIELD OF UNDESIREDBY-PRODUCTS FROM A GIVEN HYDROCARBON CHARGE, WHICH COMPRISES CONTACTINGSAID CHARGE UNDER CRACKING CONDITIONS WITH A CATALYST COMPOSITIONCOMPRISING AN INORGANIC OXIDE MATRIX HAVING DISPERSED THEREIN ANALUMINOSILICATE HAVING AN ORDERED CRYSTALLINE STRUCTURE AND CONTAININGFROM 0.5 TO 1.0 EQUIVALENT PER GRAM ATOM OF ALUMINUM OF IONS OF POSITIVEVALENCE WHEREIN THE ENHANCED SELECTIVITY OF SAID CATALYST COMPOSITIONARISES FROM THE FACT THAT THE ALUMINOSILICATE HAS ASSOCIATED THEREWITHBOTH HYDROGEN IONS AND CATIONS OF METALS SELECTED FROM GROUP IB THROUGHGROUP VIII OF THE PERIODIC TABLE.